Novel process for promoting hydrosilation reactions using a second hydrosilane

ABSTRACT

In the process of preparing compounds containing silicon-carbon bonds by the hydrosilation reaction of a hydrosilyl reactant with an olefinic reactant in the presence of a soluble platinum catalyst, the improvement which comprises operating the process at a temperature below 150° C. and employing, as a reaction promoter, a hydrosilyl compound whereby said hydrosilyl reactant has a composition different from the composition of said promoter and whereby said promoter provides (i) a 20% increase in the amount of silicon-carbon compounds, or (ii) a 20% increase in reaction rate relative to an unpromoted reaction.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to novel processes for improving rates and yields in hydrosilation reactions, those being addition reactions of compounds containing hydrosilyl groups, i.e., .tbd.SiH groups, to unsaturated compounds to form carbon-functional silicon compounds. In particular, the present invention relates to the use of a hydrosilyl compound as a promoter in these hydrosilation reactions.

2. Prior Art

The hydrosilation reaction was discovered in 1947 and is now one of the best known and most widely practiced reactions in organosilicon chemistry, including use in a wide variety of large scale commercial applications. This reaction has been the subject of several extensive reviews. l C. Earborn & R. W. Bott, Organometallic Compounds of the Group IV Elements (1968); E. Lukevics & M. G. Voronkov, Organic Insertion Reactions of Group IV Elements (1966).

A number of patents in the art have shown that platinum compounds can have important catalytic effects in these reactions.

U.S. Pat. No. 2,632,013 to Wagner et al, for example, is an early patent showing that various forms or compounds of platinum can be effective catalysts for hydrosilation reactions. U.S. Pat. No. 2,823,218 to Speier showed that chloroplatinic acid, a soluble form of platinum, was a particularly effective catalyst. A variety of additives to or derivatives of chloroplatinic acid have been claimed as offering some advantage over chloroplatinic acid, H₂ PtCl₆. None of these patents teaches the use of a second hydrosilyl compound used in combination with the soluble platinum catalyst to promote the rate or yields of the first reaction.

Of the many hydrosilation reactions taught in the prior art, very few involve the hydrosilation reactions between two different hydrosilyl compounds and one unsaturated compound. Moreover, that art which does discuss this area focuses on the competitive reactivity order of the hydrosilyl compounds with regard to the unsaturated compound. That is, the art teaches which of the two hydrosilyl compounds reacts better with a third unsaturated one; there is no teaching of the positive effect one such hydrosilyl compound might have on the other in increasing the yield of the hydrosilation reaction product, i.e., the product of the reaction between the hydrosilyl reactant and the unsaturated compound, or in decreasing the reaction time in the formation of such product.

For example, work by Bailey, D. L. Bailey, remarks at the 137th National Meeting of the American Chemical Society (Apr. 5-14, 1960), and by Benkeser, R. A. Benkeser, remarks at the 165th National Meeting of the American Chemical Society (Apr. 8-13, 1973), has established the competitive reactivity order H₃ SiCl>H₂ SiCl₂ >Cl₃ SiH for reactions with alkenes, this being the reverse of the reactivity order these compounds display when they are not competing with one another. The reversal occurs because the compounds, which are more reactive competitively, effectively reduce the reactivity of the other compounds, i.e., they have a negative effect on hydrosilation reactivity. The work done by Bailey did not study and did not note any promotional effects.

Other studies, have also concentrated on the competitive effect among hydrosilyl reactants. Ponomarenko et al in Izv. Akad. Nauk SSSR, Otdel. Khim. Nauk 1610 (1960); Engl. trans. in Bull. Acad. Sci. USSR, Chem. Sci. Section 1496 (1960).

In none of this prior art is there found an example of a second hydrosilyl compound having a positive effect on the reactivity of another hydrosilyl compound. This prior art always shows the two compounds in competition with one another rather than the one promoting the other in a non-competitive hydrosilation reaction.

Two Russian papers by Ponomarenko et al. do note such a positive effect, whereby Cl₃ SiH and EtSiHCl₂ increase yields of products from reactions of Et₂ MeSiH with allyl ethers (CH₂ ═CH--CH₂ OCF₂ CFClH or CH₂ ═CHCH₂ OCF₂ CF₂ H) using Pt/C (platinum on carbon) catalyst. In these cases, however, high temperatures (164°-198° C.) and long reaction times (3 hrs) were used. These studies also involved the use of insoluble platinum catalysts. The same workers reacted Et₂ MeSiH with CH₂ ═CHCH₂ OCF₂ CF₂ H using H₂ PtCl₆ at lower temperature/time (25° C./30 min), but did not use a second hydrosilyl compound in the H₂ PtCl₆ -catalyzed reaction. The authors of those papers specifically commented that no promotional effects were observed in using a second hydrosilyl compound together with chloroplatinc acid in a hydrosilation reaction conducted under mild reaction temperatures.

Thus, the use of a second hydrosilyl compound and soluble platinum catalysts to promote the large rate and/or yield enhancements disclosed in the present invention under relatively mild temperatures has not been disclosed in the prior art, and is in fact contradicted by the above prior art.

There has also been some prior art in which chloroplatinic acid, H₂ PtCl₆, has been treated with Cl₃ SiH or MeSiHCl₂ to give solutions which served as hydrosilation catalysts. Benkeser, 90 J. Am. Chem. Soc., 1871 (1968). In those studies, however, the same reactant, i.e. Cl₃ SiH, was evaluated as both the starting reactant and the promoter. No advantage in either rate or yield was found. Similarly, in studies involving MeSiHCl₂, the MeSiHCl₂ was evaluated as both the starting reactant and promoter, and again no promotional advantages were observed. In U.S. Pat. No. 3,576,027 to Fish, a catalyst was prepared by treating H₂ PtCl₆.6H₂ O with Me₂ SiHCl in a separate step, which catalyst was then isolated and used to catalyze a reaction of MeSiHCl₂ with 1-octene. The catalyst there was formed in a precombination step rather than being generated in situ. Additionally, large promotional effects were not observed. These tests show once more that it would be quite unexpected to find that a second hydrosilyl compound, used in a hydrosilation reaction at mild temperatures, could actually promote the rates and yields of that reaction.

Thus, there is a need in the art for a process which can be applied to hydrosilation reactions, i.e., those between hydrosilyl groups and unsaturated compounds, which process is characterized by relatively mild temperatures and relatively fast rates, by relatively inexpensive catalysts from which the active catalysts of the invention are generated in situ, and by greatly enhanced yields of carbon-functional silicon compounds formed from the hydrosilation reaction.

OBJECTS

It is thus an object of this invention to provide a process for improving the yields and rates of hydrosilation reactions under relatively mild conditions using a second hydrosilyl promoter.

It is a further object of this invention to provide such a process employing relatively inexpensive catalysts, such as soluble platinum catalysts. An even further object of the invention is to provide such a process whereby the active catalyst is generated in situ.

Another object of the invention is to provide such a process in which the reaction scale is not limited by size and may range from several grams to several thousand kilograms.

A still further object of this invention is to provide such a process where the active catalyst can be useful at sub-ambient temperatures thereby enabling the reactions to be run at ambient pressures, obviating the need for pressure-resistant equipment.

Other objects and advantages of the invention will become apparent as the description proceeds.

BRIEF SUMMARY OF THE INVENTION

In satisfaction of the foregoing objects, this invention relates to a process for greatly improving the reaction rates and yields/selectivities in hydrosilation reactions, i.e., reactions of compounds containing hydrosilyl groups with unsaturated compounds to form carbon-functional silicon compounds: ##STR1##

Specifically, this invention is based on the unexpected discovery that a second hydrosilyl compound promotes the hydrosilation reaction when reacted with soluble platinum compounds, e.g., chloroplatinic acid. The hydrosilyl promoter generates an active catalyst in situ, and thus no synthetic work, isolation or purification is involved in generating such catalyst as in prior art catalysts. The promoter, for example, need not be isolated by expensive ligands and is thus less expensive as well as more effective than catalysts which are bound by these ligands.

In addition, the use of the hydrosilyl promoter eliminates the induction period associated with the use of H₂ PtCl₆ thus resulting in large rate increases in certain cases. This elimination of the induction period can also make external heating unnecessary and result in large energy savings. The hydrosilyl promoter further results in substantial improvements in product selectivity in certain hydrosilation reactions, thus increasing the commercial utility of such reactions and, in combination with the large reaction rate increases mentioned above, significantly increasing effective production capacity without building additional production facilities.

Finally, an important and novel aspect of th invention is that, in certain cases, the hydrosilyl promoter can be useful at sub-ambient temperatures. This enables some reactions to be run at ambient pressure, obviating the need for pressure-resistant equipment.

Thus the key discovery of the invention is the use of a hydrosilyl promoter in a platinum-catalyzed hydrosilation reaction which surprisingly increases catalytic effectiveness.

Although the degree to which the promotional effects may vary depending on which hydrosilyl reactant, hydrosilyl promoter, platinum compound or unsaturated olefin is selected, the invention is characterized by increases in yield or selectivity of at least 20 percent. The most striking or positive promotion effects, in terms of reaction rate and selectivity, are observed from those reactions in which the electron environment of the hydrosilyl promoter is most nearly opposite the electron environment of the hydrosilyl starting reactant. Further, strong promotional effects are observed in reactions which are normally sluggish, i.e., those which require extended heating or high catalyst levels.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a hydrosilation process having improved rates and yields as a result of the use of a hydrosilyl promoter. This promoter reacts with a soluble platinum catalyst and a starting hydrosilyl reactant to greatly increase the yield, selectivity or rate of the hydrosilation product.

While not wishing to be bound by theory, the active catalyst is believed to be generated when platinum catalysts such as chloroplatinic acid undergo a series of reactions involving both the hydrosilyl reactant and the hydrosilyl promoter to produce a species containing Pt--Si bonds. The following is a possible representation of such reactions involving Cl₃ SiH and Et₃ SiH as the promoter and reactant, respectively. The Pt--Cl is one such group in a soluble Pt catalyst containing Pt--Cl bonds, such as H₂ PtCl₆ :

    Pt--Cl+Et.sub.3 SiH→Et.sub.3 SiCl+Pt--H

    Pt--H+Cl.sub.3 SiH→H.sub.2 +Pt--SiCl.sub.3

It has been reported that Et₃ SiH reacts with Pt--Cl bonds as shown, while Cl₃ SiH does not. It has also been reported that Cl₃ SiH reacts with Pt--H bonds to form H₂ and Pt--SiCl₃ bonds, while Et₃ SiH does not undergo such a reaction. It should be noted that these reactions explain the formation of Pt--Si species by established chemistry and that such species need only to be sufficiently stable in solution to act as highly efficient hydrosilation catalysts. Such species, because of their inherently high reactivity, may not be sufficiently stable to allow isolation and identification by normal chemical methods.

The catalysts for the instant invention are platinum compounds used in the form of solutions, such as solutions of H₂ PtCl₆ (in hydrated or unhydrated form), solutions of PtCl₄ or PtCl₂, solutions of other soluble Pt compounds such as ethylene bis(platinous chloride), or Pt catalyst solutions as disclosed, for example, in U.S. Pat. No. 3,220,972. Platinum catalysts containing strongly bound stabilizing ligands such as trialkyl or triarylphosphines or acetylacetonate groups are less effective. Phosphines or other strongly bound Pt ligands appear to interfere with the mutual interaction of hydrosilyl promoter and hydrosilyl reactant with the platinum catalyst, preventing or retarding the formation of the active catalyst species of the present invention.

Because of its availability and relatively low cost (for platinum compounds), chloroplatinic acid is the preferred catalyst, although other soluble platinum compounds such as PtCl₄ and ethylene bis(platinous chloride) are considered equally effective.

The platinum solution is added to the reaction in a concentration range of 10⁻³ to 10⁻⁸ molar relative to the combined starting reactant and promoter, preferably 10⁻⁴ to 10⁻⁶ molar.

The olefinic coreactant may be any one of a variety of functional or non-functional terminally unsaturated compounds and has the general formula CH₂ ═C<. The following are examples of compounds whose hydrosilation reactions can be promoted via processes of the instant invention:

CH₂ ═CYCH₂ Cl CH₂ ═CYCH₂ OR where

Y═H or R as defined below for hydrosilyl reactant

CH₂ ═CYCMe₃ CH₂ ═CYCH₂ CHMe₂

CH₂ ═CYφ CH₂ ═CYCH₂ OAc

CH₂ ═CYOAc CH₂ ═CYCH₂ O₂ CCY═CH₂

CH₂ ═CYCH₂ O₂ CY CH₂ ═CYO₂ CY

CH₂ ═CHCHYCl CH₂ ═CYCH₂ CN

Thus included are allyl and methallyl compounds, vinyl compounds, terminal alkenes, including halides, ethers, esters, nitriles, and the like, with the proviso that when the olefinic reactant is substituted to functional groups, said functional groups do not interfere with the promotion mechanism of the hydrosilation reaction. The allyl and methallyl compounds include the allyl and methallyl polyalkylene oxide ethers typical of those used commercially to prepare silicone-polyether copolymers.

The olefinic coreactant is used at 0.1-2.0 molar amounts relative to the hydrosilyl reactant, more preferably 0.5-1.5 and most preferably 0.8-1.2 molar amounts.

The hydrosilyl reactant of this invention is a silicon-bonded hydrogen reactant having the general formula R₃ SiH where each R represents the same or different monovalent hydrocarbon group, aliphatic having 1-10 carbon atoms or aromatic having 6-20 carbon atoms free of terminal unsaturation, possibly substituted with functional groups such as halogen, cyano, carboalkoxy (ester), ether, thioether, or the like, with the proviso that when such hydrosilyl reactant is substituted with functional groups, said functional groups do not interfere with the promotion mechanism for hydrosilane-promoted hydrosilations. R may be alkyl, aryl, alkoxy, acyloxy or carbamoyloxy when R is a hydrocarbon group as defined above. Alternatively, R may be halogen, i.e., Cl₃ SiH or siloxy.

Illustrative hydrosilyl reactants include hydrosilanes such as triethylsilane, a hydrochlorosilane such as Cl₃ SiH, a hydrosiloxane such as (Me₃ SiO)₂ SiMeH, or a polyhydrosiloxane containing hydrosilyl groups at either internal or terminal positions, or both.

The following represent hydrosilyl reactants of the hydrosilane type whose hydrosilation reactions may be promoted with a hydrosilyl promoter:

    ______________________________________                                         Me.sub.3 SiH                                                                             MeEt.sub.2 SiH                                                                             Me.sub.2 EtSiH                                                                             Et.sub.3 SiH                                 Pr.sub.3 SiH                                                                             φ.sub.3 SiH                                                                            φ.sub.2 MeSiH                                                                          φSiMe.sub.2 H                            ______________________________________                                    

Illustrative of the hydrosiloxanes are the following: ##STR2## and the like where Me groups can be replaced by functional groups free of terminal unsaturation and which do not otherwise interfere with the promotion mechanism, such as haloalkyl, cyanoalkyl, phenylalkyl, acyloxyalkyl, etc.

Other hydrosilyl reactants include halosilanes, hydroalkoxysilanes and hydroacyloxysilanes, of which the following are representative:

Cl₃ SiH F₃ SiH Br₃ SiH MeSiHCl₂

Me₂ SiHCl MeSiHF₂ Me₂ SiFH MeSiHBr₂

Me₂ SiHBr Me(MeO)₂ SiH (MeO)₃ SiH

Me(MeCO₂)₂ SiH (EtO)₃ SiH

In another embodiment of the invention, two R-groups taken together may form a hetero-cyclic ring including the silicon atoms, as in ##STR3## where n=3-6.

The structure of the hydrosilyl reactant may thus vary widely including but not being limited to the structures shown above, which merely exemplify some of the possibilities.

The hydrosilyl promoter may also be a hydrosilane, a hydrochlorosilane, or a hydrosiloxane exactly as defined above for the hydrosilyl reactant, with the proviso that the hydrosilyl promoter and the hydrosilyl reactant may not be the same compound when used in the same reaction. As noted above, the most effective promotion effects are observed when the hydrosilyl reactant and the hydrosilyl promoter differ substantially in structure, or in the electronic environment of the respective .tbd.SiH groups. Preferably, hydrosilyl promoter is selected from the group consisting of Cl₃ SiH, MeSiHCl₂, Me₂ SiHCl, Et₃ SiH, F₃ SiH and Br₃ SiH.

The hydrosilyl promoter can be used in a wide range of concentrations relative to the hydrosilyl reactant or the olefinic or unsaturated coreactant. The hydrosilyl promoter is used at 0.0001-2.0 molar amounts relative to the hydrosilyl reactant, more preferably 0.0001-0.1 molar amounts. The greatest advantages from a commercial standpoint are attained when very low concentrations of hydrosilyl promoter are effective. In most cases, even with small amounts of promoter, it can simply be added to the hydrosilyl reactant and the platinum catalyst.

While the reactants, catalyst, and promoter can generally be combined in total and allowed to react, there are specific cases in which it is advantageous to vary the order of combination of either reactant, or the promoter, or combinations thereof, to obtain maximum degree of promotion. For example, promotion of the reaction between Et₃ SiH and allyl chloride by Cl₃ SiH appears to be optimum when a 10/1 molar mixture of allyl chloride/Cl₃ SiH is added to Et₃ SiH containing the chloroplatinic acid.

The reaction process of this invention may reach a reaction temperature as high as 150° C., although temperatures below 100° C. are preferred. The reaction can also be promoted at sub-ambient temperatures.

The reaction can be run under a pressurized atmosphere as high as 10 atmospheres in pressure. Alternatively, if, for example, the reaction is run at sub-ambient temperatures, the reaction can be run at ambient pressures.

Finally, the reaction may be run in time periods ranging from minutes to hours in duration, preferably 3-1000 minutes, more preferably 5-300 minutes and most preferably 10-100 minutes.

Not all reactions between hydrosilyl reactants and unsaturated compounds are promoted by all hydrosilane promoters. Within the almost infinite number of possible combinations of hydrosilane reactants, unsaturated reactants, and hydrosilane promoters, and the possible variations in reaction conditions, i.e., temperature, sequence of combination, relative concentrations, etc., under which these three components can be reacted, there will be combinations for which promotion effects are not observed. A greater element of predictability, however, can be found by controlling certain variables. The most effective promotion effects, for example, are observed when the hydrosilyl reactant and the hydrosilyl promoter differ substantially in structure, or in electronic environment of the respective .tbd.SiH groups. For example, Cl₃ SiH, which has strong electron attracting halogen groups, is an effective promoter for hydrosilation reactions of trialkylsilanes, such as Et₃ SiH. Conversely, Et₃ SiH is an effective promoter for hydrosilation reactions of Cl₃ SiH.

The conditions and variables for optimal promotional effect can be readily ascertained to one skilled in the art from the disclosure and examples herein. The reactions encompassed within the present invention are characterized by increases in either rate or selectivity of at least 20%.

EXAMPLES

The following specific examples and procedures are presented to illustrate the invention, but are not to be construed as limiting thereon. The examples representing this invention are numbered; those examples that are lettered are comparative examples which do not illustrate the invention. Only those examples which satisfied the requirements of 20% yield or reaction rate improvement were numbered.

Reported yields are in molar percentages and, in most examples, are given only for the desired hydrosilation product. Other by-products are obtained in many of the examples; their yields are not reported therein.

In the examples and throughout the specification, all temperatures are on the Centigrade Scale (°C.), and all percentages and parts are on a molar basis unless specified otherwise.

    ______________________________________                                         Definitions                                                                    ______________________________________                                         %             percent                                                          Pt            platinum                                                         wt            weight                                                           g             gram or grams                                                    Mol-%         mole percent                                                     EqM           Equimolar                                                        min. or mins  minute or minutes                                                hr or hrs     hour or hours                                                    sec           seconds                                                          ml            milliliter                                                       mm            millimeters of mercury pressure                                  Ac            COCH.sub.3                                                       C.sub.6 H.sub.5                                                                              phenyl                                                           Me            methyl                                                           Et            ethyl                                                            VPC           vapor phase chromatography                                       NMR           nuclear magnetic resonance                                       D.sub.3 D'    heptamethylcyclotetrasiloxane:                                                  ##STR4##                                                                      or the corresponding derivative                                                 ##STR5##                                                        MD'M          heptamethyltrisiloxane:                                                         ##STR6##                                                                      or the corresponding derivative:                                                ##STR7##                                                        ______________________________________                                    

GENERAL PROCEDURE

All the reactions above were run in standard laboratory glassware of flasks of various sizes as noted in each example using magnetic stirring under nitrogen atmosphere with heat being applied by electric mantles. Flasks were also fitted with Hopkins condensers and thermometers, temperatures being recorded in Centigrade. All reaction products were identified by vapor phase chromatography (VPC) and nuclear magnetic resonance (NMR) spectroscopy. Reported yields were based on the amount of hydrosiloxane or hydrosilane charged.

SPECIFIC PROCEDURES Comparative Example A

Reaction of D₃ D' with methallyl chloride; reactants combined at start.

In a 200 ml apparatus, there were combined 56.4 g (0.2 mol) of D₃ D', 20.0 g (0.22 mol) of methallyl chloride, and 0.2 ml of a reduced platinum catalyst (prepared according to Example 1, U.S. Pat. No. 3,220,972). Heat was applied to about 80° C. when an exothermic reaction occurred to a maximum temperature of 141° C. Reaction was complete after 1 hr., 17 mins. and was followed by cooling. The reaction mixture was suction filtered into a 100 ml flask which was fitted for vacuum distillation. The following products were isolated:

    ______________________________________                                                          Boiling                                                                        Point/                                                        Product          Pressure   g        Yield                                     ______________________________________                                         D.sub.3 D'Cl     76°/17 mm                                                                          17.0     27.0%                                                      (aspirator)                                                   D.sub.3 D'CH.sub.2 C(CH.sub.3)═CH.sub.2                                                     80°/17 mm                                                                          3.0       4.4%                                                      (aspirator)                                                   D.sub.3 D'CH.sub.2 CH(CH.sub.3).sub.2                                                           80°/17 mm                                                                          1.6       2.4%                                                      (aspirator)                                                   D.sub.3 D'CH.sub.2 CH(CH.sub.3)CH.sub.2 Cl*                                                     60°/0.25 mm                                                                        44.8     60.0%                                     Heavies          --         1.2      --                                        ______________________________________                                          *The yield of the desired hydrosilation product by this route was 60.0%  

Comparative Example B

Reaction of equimolar mixture of D₃ D'/MD'M with methallyl chloride.

In a 100 apparatus, there were combined 30.5 g (0.1 mol) of 92% D₃ D', 22.2 g (0.1 mol) of MD'M, and 9.1 g (0.1 mol) of methallyl chloride, followed by 0.05 mol of Pt catalyst solution. Heat was applied to 100° C. over 152 min, when an exothermic reaction occurred to 130° C. Vacuum distillation of the complete reaction yielded 4.26 g (13.6%) of M₂ D'CH₂ CHMeCH₂ Cl and 21.37 g (57.4%) of D₃ D'CH₂ CHMeCH₂ Cl. This example shows that neither D₃ D' nor MD'M is an effective promoter for reaction of the other with methallyl chloride at the equimolar level.

Comparative Example C

Reaction of D₃ D' with methallyl chloride; olefin added to hydrosiloxane.

In a 500 ml apparatus were placed 282 g (1.0 mol) of D₃ D' which was heated to 85° C., followed by addition of 0.3 ml of a solution of 4.0 wt.% of H₂ PtCl₆.6H₂ O in 1,2-dimethoxyethane. Dropwise addition of 90.5 g (1.0 mol) of methallyl chloride was begun and continued at a rate which maintained the reaction temperature at 87°-93° C. Addition was complete in 1.5 hr., and the reaction mixture was distilled directly, yielding the following products:

    ______________________________________                                                         Boiling                                                                        Point/                                                         Product         Pressure   g         Yield                                     ______________________________________                                         D.sub.3 D'Cl    77°/17 mm                                                                          55.0      17.4%                                                     (aspirator)                                                    D.sub.3 D'CH.sub.2 C(CH.sub.3)═CH.sub.2                                                    31°/0.2 mm                                                                         trace     --                                        D.sub.3 D'CH.sub.2 CH(CH.sub.3).sub.2                                                          31°/0.2 mm                                                                         30.5       9.0%                                     D.sub.3 D'CH.sub.2 CH(CH.sub.3)CH.sub.2 Cl*                                                    55°/0.12 mm                                                                        246.2     66.1%                                     Heavies         --         11.0      --                                        ______________________________________                                          *The yield of the desired hydrosilation product was 66.1%, a relative          improvement of 10.2% over the 60.0% obtained in Comparative Example A.   

Example 1

Reaction of equimolar mixture of D₃ D'/Cl₃ SiH with methallyl chloride.

In a 50 ml apparatus there were combined 24.7 g (0.085 mol) of D₃ D', 11.4 g (0.085 mol) of Cl₃ SiH, and 7.7 g (0.085 mol) of methallyl chloride. Pt catalyst solution (0.05 ml) was added at 20° C. causing a gentle exothermic reaction to 78° C. in 10 min. Reaction was complete in 15 min. The yield of D₃ D'CH₂ CHMeCH₂ Cl as analyzed by VPC was greater than 90%, a substantial improvement over the yields of Comparative Examples A, B and C, and a demonstration of non-competitive promotion by Cl₃ SiH of hydrosiloxane reactivity.

Example 2

Reaction of D₃ D' with methallyl chloride promoted by 9 mol-% Cl₃ SiH.

In the apparatus of Example 3, there were combined 30.5 g of 92% D₃ D' (8% D₄, 0.1 mol of D₃ D'), 9.1 g (0.1 mol) of methallyl chloride, and 0.5 g Cl₃ SiH. Pt catalyst solution (0.05 ml) was added at 20° C.; after 42 min. temperature was 29° C. and 0.7 g additional Cl₃ SiH was added. Reaction temperature rose gradually to 107° C. over 87 min, when reaction was complete. Vacuum distillation yielded 32.85 g (88.2%) of D₃ D'CH₂ CHMeCH₂ Cl, the yield being similar to that of Example 1 which employed a much larger amount of Cl₃ SiH promoter.

Example 3

Reaction of D₃ D' with methallyl chloride promoted by 11 mol-% Cl₃ SiH at 50° C.

The reaction of Example 2 was repeated except that 1.5 g Cl₃ SiH was added at the start and the reaction mixture was heated to 50° C. prior to addition of Pt catalyst. There was a rapid exothermic reaction to 148.5° C. in 7 min at which point the reaction was complete, yielding 28.49 g (76.5%) of D₃ D'CH₂ CHMeCH₂ Cl on distillation. The lower yield relative to Examples 1 and 2, and the higher amount of non-volatile products (11.5% of total) indicate little advantage to adding catalyst at the higher temperature.

Example 4

Reaction of equimolar mixture of D₃ D'/MeSiHCl₂ with methallyl chloride.

In a 50 ml apparatus, there were combined 9.7 g (0.085 mol) of MeSiHCl₂, 24.2 g (0.085 mol) of D₃ D', and 7.8 g (0.085 mol) of methallyl chloride. Pt catalyst solution (0.05 ml) was added at 20° C. Heat was applied intermittently causing an exothermic reaction to 75° C. after 26 min. Reaction was complete after 40 min, and was vacuum distilled, yielding 23.8 g (76.1%) of D₃ D'CH₂ CHMeCH₂ Cl. This example shows that MeSiHCl₂ is slightly less effective than Cl₃ SiH as a promoter for the reaction of D₃ D' with methallyl chloride.

Comparative Example D

Reaction of equimolar mixtures of D₃ D'/Et₃ SiH with methallyl chloride.

In a 100 ml apparatus, there were combined 28.4 g (0.1 mol) of 98% D₃ D', 11.6 g (0.1 mol) of Et₃ SiH, and 9.1 g (0.1 mol) of methallyl chloride. Pt catalyst solution (0.05 ml) was added at 21° C. Heat was applied to 99° C. over 108 min, when a later exothermic reaction to 118° C. occurred. Reaction was complete and was vacuum distilled, yielding 24.3 g (65.2%) of D₃ D'CH₂ CHMeCH₂ Cl. This example shows that Et₃ SiH is much less effective than Cl₃ SiH or MeSiHCl₂ as a promoter for the reaction of D₃ D' with methallyl chloride when used at the equimolar level.

Comparative Example E

Reaction of D₃ D' with methallyl chloride promoted by 10 mol-% MeSiCl₃.

In a 50 ml apparatus, there were combined 30.5 g (0.1 mol) of 92% D₃ D', 9.1 g (0.1 mol) of methallyl chloride, and 1.5 g (0.01 mol) of MeSiCl₃. Pt catalyst solution (0.05 ml) was added at 21° C. Heat was applied to 89° C. over 41 min followed by a gentle exothermic reaction to 123.5° C. Reaction was complete in 45 min, and was vacuum distilled, yielding 26.6 g (71.4%) of D₃ D'CH₂ CHMeCH₂ Cl. This example shows that MeSiCl₃ is not as effective as either Cl₃ SiH or MeSiHCl₂ in promoting the reaction of D₃ D' with methallyl chloride, although it did demonstrate a positive effect.

Comparative Example F

Reaction of equimolar mixture of D₃ D'/Me₂ SiHCl with methallyl chloride.

In a 100 ml apparatus, there were combined 30.5 g (0.1 mol) of 92% D₃ D', 9.1 g (0.1 mol) of methallyl chloride, and 9.5 g (0.1 mol) of Me₂ SiHCl. Heat was applied to 43° C. and 0.05 ml Pt catalyst solution added, causing an exothermic reaction to 95.5° C. in 26 min, with the heat source removed. Vacuum distillation of the complete reaction yielded 7.82 g (42.3%) of Me₂ SiClCH₂ CHMeCH₂ Cl and 16.89 g (45.3%) of D₃ D'CH₂ CHMeCH₂ Cl. This example shows that neither Me₂ SiHCl nor D₃ D' is an effective promoter for reaction of the other with methallyl chloride when used at the equimolar level.

                                      TABLE I                                      __________________________________________________________________________     PROMOTION OF D.sub.3 D ' AND METHALLYL CHLORIDE                                Example                                                                             REACTANT A                                                                             OLEFIN   PROMOTER  YIELD %                                                                              TIME                                     __________________________________________________________________________     Comp. A                                                                             D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                             --       60*   77 min                                   Comp. B                                                                             D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. MD'M 57.4  152                                                                               min                                   Comp. C                                                                             D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                             --       66.1  90 min                                   1    D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Cl.sub.3 SiH                                                                        >90   15 min                                   2    D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            9 mol % Cl.sub.3 SiH                                                                      88.2**                                                                              87 min                                   3    D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            11 mol % Cl.sub.3 SiH                                                                    76.5  7  min                                   4    D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. MeSiHCl.sub.2                                                                       76.1  40 min                                   Comp. D                                                                             D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Et.sub.3 SiH                                                                        65.2  108                                                                               min                                   Comp. E                                                                             D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            10 mol % MeSiCl.sub.3                                                                    71.4  45 min                                   Comp. F                                                                             D.sub.3 D'                                                                             CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Me.sub.2 SiHCl                                                                        45.3***                                                                            26 min                                   __________________________________________________________________________      *When Olefin was added to hydrosiloxane in dropwise manner rather than th      reactants being combined at the start as in Comparative Example A, the         yield was 66.1% (see Comparative Example C).                                   **When mixture was heated to 50° C. (versus 20° C.) prior t      addition of Pt catalyst solution, yield was 76.5% indicating little            advantage to adding catalyst at high temperature in this reaction (see         Example 3).                                                                    ***Me.sub.2 SiHCl competed rather than promoted production with D.sub.3        D'.                                                                      

This table shows that yields and rates of D₃ D' can be greatly improved depending on the nature and quantity of the promotor. Example 1 shows the most dramatic increase, relative to an unpromoted reaction, in both yield (greater than 30% absolute) and rate when using equimolar Cl₃ SiH. Using a much smaller quantity of Cl₃ SiH, i.e., equimolar versus 9 mol-%, gave substantially equivalent yields even though the rate of the reaction was not diminished (compare Example 1 to Example 2). As observed from this table, order of reactivity for greatest yield production is as follows: Cl₃ SiH>MeSiHCl₂ >MeSiCl₃ >Et₃ SiH>Me₂ SiHCl.

Comparative Example G

Reaction of MD'M with methallyl chloride; reactants combined at start.

In the apparatus of Comparative Example A, there were combined 43.1 (0.194 mol) of MD'M, 19.0 g (0.21 mol) methallyl chloride, and 0.32 ml of the catalyst used in Comparative Example A. Heat was applied to 94° C. at which point the reaction mixture was refluxing. The reflux temperature increased over 2 hrs. to 143° C. The product mixture was transferred to a 100 ml flask and distilled, yielding the following products:

    ______________________________________                                                           Boiling                                                                        Point/                                                       Product           Pressure  g        Yield                                     ______________________________________                                         Unreacted MD'M    41°/17 mm                                                                          5.9     13.7%                                                       (aspirator)                                                  M.sub.2 D'Cl      50°/17 mm                                                                         16.5     32.2%                                                       (aspirator)                                                  M.sub.2 D'CH.sub.2 C(CH.sub.3)═CH.sub.2                                                      56°/17 mm                                                                          3.9      7.1%                                                       (aspirator)                                                  M.sub.2 D'CH.sub.2 CH(CH.sub.3).sub.2                                                            --        nil      --                                        M.sub.2 D'CH.sub.2 CH(CH.sub.3)CH.sub.2 Cl*                                                      36°/0.3 mm                                                                        21.3     34.1%                                     Heavies           --         2.2                                               ______________________________________                                          *The yield of the desired hydrosilation product was 34.1%. The yields          obtained compare favorably with those reported by Davis (J. Org. Chem.         38,838 (1973)) which were: M.sub.2 D'CH.sub.2 C(CH.sub.3)═CH.sub.2         (9%), and M.sub.2 D'CH.sub.2 CH(CH.sub.3)CH.sub.2 Cl (34%) wherein the         reactants were combined at the start.                                    

Comparative Example H

Reaction of MD'M with methallyl chloride; olefin added to hydrosiloxane.

In a 100 ml flask, there were placed 39.1 g (0.176) mol) of MD'M which was heated to 75°, when 0.1 ml of the catalyst used in Comparative Example A was added. Addition of 16.3 g (0.18 mol) of methyallyl chloride was begun, with reaction proceeding slowly for 30 mins., followed by an exothermic temperature rise to 119°. Reaction was complete after 1.5 hrs. from start of addition. Direct vacuum distillation yielded the following products:

    ______________________________________                                                          Boiling                                                                        Point/                                                        Product          Pressure   g        Yield                                     ______________________________________                                         M.sub.2 D'Cl     50°/17 mm                                                                          7.9      17.5%                                                      (aspirator)                                                   M.sub.2 D'CH.sub.2 C(CH.sub.3)═CH.sub.2                                                     31°/0.22 mm                                                                        0.7       1.4%                                                      (aspirator)                                                   M.sub.2 D'CH.sub.2 CH(CH.sub.3).sub.2                                                           31°/0.22 mm                                                                        4.9      10.0%                                     M.sub.2 D'CH.sub.2 CH(CH.sub.3)CH.sub.2 Cl*                                                     33°/0.18 mm                                                                        27.6     50.2%                                     Heavies          --         3.7                                                ______________________________________                                          *The yield of the desired hydrosilation product was 50.2%, a relative          improvement of 47.2% over the 34.1% obtained in Comparative Example C or       the 34% reported by Davis.                                               

Example 5

Reaction of equimolar mixture of MD'M/Cl₃ SiH with methallyl chloride.

In a 100 ml apparatus, there were combined 11.1 g (0.05 mol) of MD'M, 4.5 g (0.05 mol) of methallyl chloride, and 6.8 g (0.05 g mol) of Cl₃ SiH. Pt catalyst solution (0.01 ml) was added at 40° C., causing a violent exothermic reaction to more than 100° C. in 1 min. Vacuum distillation of the complete reaction yielded 12.78 g (81.8%) of M₂ D'CH₂ CHMeCH₂ Cl, indicating that Cl₃ SiH is an effective promoter for the reaction of MD'M with methallyl chloride. The yield here is significantly higher than in Comparative Examples G or H, and the reaction time much shorter. Note that MD'M and D₃ D' are chemical models for polyhydrosiloxane fluids which are articles of commerce, demonstrating clearly that reactions of such fluids with methallyl chloride will also be promoted.

Example 6

Reaction of equimolar mixture of MD'M/MeSiHCl₂ with methallyl chloride.

In a 100 ml apparatus, there were combined 16.7 g (0.075 mol) of MD'M, 8.6 g (0.075 mol) of MeSiHCl₂, and 6.8 g (0.075 mol) of methallyl chloride, followed by addition of 0.01 ml Pt catalyst solution at 48° C. There was an exothermic reaction to 92° C. in 9 min, with the reaction being complete in 50 min. Vacuum distillation yielded 16.57 g (70.7%) of M₂ D'CH₂ CHMeCH₂ Cl, showing that MeSiHCl₂ is slightly less effective than Cl₃ SiH as a promoter for the reaction of MD'M with methallyl chloride at the equimolar level.

Example 7

Reaction of equimolar mixture MD'M/Et₃ SiH with methallyl chloride.

In a 100 ml apparatus, there were combined 11.1 g (0.05 mol) of MD'M, 5.8 g (0.05 mol) of Et₃ SiH, and 4.5 g (0.05 mol) of methallyl chloride, followed by addition of 0.01 ml Pt catalyst solution at 55° C. Heat was applied over 80 min to 95° C. when reaction was complete. Distillation yielded 51.3% of M₂ D'CH₂ CHMeCH₂ Cl, indicating that Et₃ SiH is not a very effective promoter for the reaction of MD'M with methallyl chloride when used at the equimolar level.

Comparative Example I

Reaction of equimolar mixture MD'M/Me₂ SiHCl with methallyl chloride.

In a 100 ml apparatus, there were combined 22.3 g (0.1 mol) of MD'M, 9.5 g (0.01 mol) of Me₂ SiHCl, and 9.1 g (0.1 mol) of methallyl chloride, followed by 0.015 ml Pt catalyst solution at 50° C. There was an exothermic reaction to 96° C. in 6 min. The complete reaction was vacuum distilled yielding 13.28 g (71.8%) of Me₂ SiClCH₂ CHMeCH₂ Cl and 8.63 g (27.6%) of M₂ D'CH₂ CHMeCH₂ Cl. This example indicates that neither MD'M nor Me₂ SiHCl is an effective promoter for reaction of the other with methallyl chloride when used at the equimolar level. The yield based on methallyl chloride was 99.4%, indicating very efficient reaction of the olefinic reactant.

                                      TABLE II                                     __________________________________________________________________________     PROMOTION OF MD'M AND METHALLYL CHLORIDE                                       Example                                                                             REACTANT A                                                                              OLEFIN   PROMOTER YIELD %                                                                              TIME                                     __________________________________________________________________________     Comp. G                                                                             MD'M     CH.sub.2 ═CMeCH.sub.2 Cl                                                             --      34.1* 120                                                                               min                                   Comp. H                                                                             MD'M     CH.sub.2 ═CMeCH.sub.2 Cl                                                             --      50.2  90 min                                   5    MD'M     CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Cl.sub.3 SiH                                                                       81.8  1  min                                   6    MD'M     CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. MeSiHCl.sub.2                                                                      70.7  50 min                                   7    MD'M     CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Et.sub.3 SiH                                                                       51.3  80 min                                   Comp. I                                                                             MD'M     CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Me.sub.2 SiHCl                                                                     27.6.sup.+                                                                           6  min                                   __________________________________________________________________________      *When Olefin was later added to hydrosiloxane rather than at start, the        yield was 50.2% (see Comparative Example H).                                   .sup.+ Me.sub.2 SiHCl competed rather than promoted production with MD'M.

As can be seen from Table II, Cl₃ SiH is again the best promoter (almost 300% relative increase) in the reaction of MD'M with methallyl chloride to produce M₂ D'CH₂ CHMeCH₂ Cl. This increased yield is particularly significantly because it represents an accurate chemical model for a commercially used polyhydrosiloxane. The order of reactivity for greatest yield production is as follows: Cl₃ SiH>MeSiHCl₂ >Et₃ SiH. As observed in Comparative Example I, Me₂ SiHCl actually interfered rather than promoted the reaction with MD'M since 71.8% of the yield was Me₂ SiClCH₂ CHMeCH₂ Cl rather than the desired M₂ D'CH₂ CHMeCH₂ Cl.

Comparative Example J

Reaction of Et₃ SiH with methallyl chloride.

A mixture of Et₃ SiH (10.5 g, 0.09 mol) and methallyl chloride (8.2 g, 0.09 mol) was combined in a 150 ml apparatus and 0.05 ml Pt catalyst solution added, followed by heating at reflux (115° C.) for 50 hr. Additional Pt catalyst solution (0.025 ml) was added at 40 hr. The incomplete reaction was distilled, yielding 4.98 g (36.8%) of Et₃ SiCl and 3.48 g (18.7%) of Et₃ SiCH₂ CHMeCH₂ Cl. This example shows that the unpromoted reaction of Et₃ SiH with methallyl chloride is very slow and endothermic.

Example 8

Reaction of equimolar mixture of Et₃ SiH/Cl₃ SiH with methallyl chloride.

In a 100 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 13.6 g (0.1 mol) of Cl₃ SiH, and 9.1 g of methallyl chloride, followed by addition of 0.05 ml Pt catalyst solution at 21° C. There was a rapid and exothermic reaction to 61° C. in 2 min. Reaction appeared to have stopped and was heated to reflux over 4 hrs. when VPC showed complete reaction. Vacuum distillation yielded 17.03 g (82.5%) of Et₃ SiCH₂ CHMeCH₂ Cl, indicating that Cl₃ SiH is an effective promoter for the reaction of Et₃ SiH with methallyl chloride.

Example 9

Reaction of Et₃ SiH with methallyl chloride promoted by 10 mol-% Cl₃ SiH.

The reaction of Example 14 was repeated except that only 1.3 g of Cl₃ SiH was used. The reaction exothermed from 21° C. to 118.5° C. in 3 min, when reaction was complete. Vacuum distillation yielded 18.2 g (88.1%) of Et₃ SiCH₂ CHMeCH₂ Cl. This example shows that the use of 10 mol-% Cl₃ SiH as promoter for the reaction between Et₃ SiH and methallyl chloride reduces reaction time by a factor of 1,000, increases the yield of the desired hydrosilation product by a factor of 5, and eliminates the need for external heating, relative to the unpromoted reaction of Comparative Example J. It also demonstrates that 10 mol-% Cl₃ SiH is more effective than equimolar Cl₃ SiH in promoting this reaction.

Comparative Example J'

Reaction of Et₃ SiH with methallyl chloride promoted by 13 mol-% MeSiCl₃.

The reaction of Example 9 was repeated except that 2.0 g MeSiCl₃ was used instead of Cl₃ SiH. The reaction was heated up to 96° C. over 8 hr, and the complete reaction vacuum distilled, yielding 10.06 g (48.7%) of Et₃ SiCH₂ CHMeCH₂ Cl. This example shows that MeSiCl₃ is a promoter but less effective than Cl₃ SiH for the reaction of Et₃ SiH with methallyl chloride.

Comparative Example L

Reaction of equimolar mixture of Et₃ SiH/MeSiHCl₂ with methallyl chloride.

In a 100 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 11.5 g (0.1 mol) of MeSiHCl₂, and 9.1 g (0.1 mol) of methallyl chloride. After heating to 50° C., the heat source was removed and 0.05 ml Pt catalyst solution added, causing an exothermic reaction to 83.5° C. in 4 min. The complete reaction was vacuum distilled, yielding 13.83 g (67.3%) of MeSiCl₂ CH₂ CHMeCH₂ Cl and 4.31 g (20.9%) of Et₃ SiCH₂ CHMeCH₂ Cl. This example shows that while MeSiHCl₂ at the equimolar level promotes the reaction between Et₃ SiH and methallyl chloride, it also competes with Et₃ SiH, reducing the yield of Et₃ SiCH₂ CHMeCH₂ Cl.

Comparative Example M

Reaction of equimolar mixture of Et₃ SiH/Me₂ SiHCl with methallyl chloride.

In a 100 ml apparatus, there were combined 7.1 g (0.075 mol) of Me₂ SiHCl, 8.7 g (0.075 mol) of Et₃ SiH, and 6.8 g (0.075 mol) of methallyl chloride. Pt catalyst solution (0.01 ml) was added at 32° C., causing an exothermic reaction to 94° C. in 4 min. Distillation of the complete reaction yielded 81.1% Me₂ SiClCH₂ CHMeCH₂ Cl and 3.6% Et₃ SiCH₂ CHMeCH₂ Cl. Et₃ SiH does promote slightly the reaction of Me₂ SiHCl with methallyl chloride.

Example 11

Reaction between Et₃ SiH and methallyl chloride promoted by Cl₃ SiH at sub-ambient temperature.

In a 50 ml apparatus, there was combined 11.6 g (0.1 mol) of Et₃ SiH, 9.1 g (0.1 mol) of methallyl chloride, and 1.4 g (0.01 mol) of Cl₃ SiH. The reaction mixture was cooled to 1° C. and was catalyzed with 0.05 ml of Pt catalyst solution. After 98 min at 1°-6° C., VPC analysis showed 47.9% conversion of reactants to Et₃ SiCH₂ CHMeCH₂ Cl with a Et₃ SiCH₂ CHMeCH₂ Cl/Et₃ SiCl selectivity ratio of 24. This example shows that Cl₃ SiH is an effective promoter for the reaction between Et₃ SiH and methallyl chloride even at sub-ambient temperatures.

Comparative Example K

Reaction of Et₃ SiH with methallyl chloride promoted by 10 mol-% Cl₃ CH.

In a 50 ml apparatus, there were combined 7.0 g (0.06 mol) of Et₃ SiH, 5.4 g (0.06 mol) of methallyl chloride, and 0.7 g (0.006 mol) of trichloromethane, followed by addition of 0.02 ml of Pt catalyst solution at 37° C. Heat was applied up to 80° C. over 2 hr. Analysis by VPC showed no reaction, indicating that Cl₃ CH is ineffective as a promoter for the reaction of Et₃ SiH with methallyl chloride. Note that Cl₃ CH is the carbon analog of Cl₃ SiH.

                                      TABLE III                                    __________________________________________________________________________     PROMOTION OF Et.sub.3 SiH AND METHALLYL CHLORIDE                               Example                                                                             REACTANT A                                                                              OLEFIN   PROMOTER  YIELD %                                                                              TIME                                    __________________________________________________________________________     Comp. J                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                             --       18.7  3000                                                                              min                                  8    Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Cl.sub.3 SiH                                                                        82.5  242                                                                               min                                  9    Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            10 mol % Cl.sub.3 SiH                                                                    88.1  3  min                                  Comp J'                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            13 mol % MeSiCl.sub.3                                                                    48.7  480                                                                               min                                  Comp K                                                                              Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            10 mol % Cl.sub.3 CH                                                                     --    120                                                                               min                                  Comp L                                                                              Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            MeSiHCl.sub.2                                                                            20.9**                                        Comp M                                                                              Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            Me.sub.2 SiHCl                                                                           3.6**                                         11   Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            10 mol % Cl.sub.3 SiH                                                                    49.7  98 min                                  __________________________________________________________________________      **In both cases, both MeSiHCl.sub.2 and Me.sub.2 SiHCl are in competition      with the reactant rather than promoting it thus accounting for the low         yields of Et.sub.3 SiCH.sub.2 CHMeCH.sub.2 Cl.                           

From Table III, it can be seen that the most dramatic improvement in yield and in time are once more with Cl₃ SiH (almost 500% relative yield increase). Another important advantage of the invention is illustrated by Example 11. Example 11 is very significant because promotion is being done at subambient temperatures. The lowest temperature tested was 0° C. but this was by no means the lower limit. This is apparently the first example of a low temperature, platinum-catalyzed hydrosilation reaction involving a trialkylsilane.

The most effective promoter tested with these reactants was Cl₃ SiH. Comparative Example K is to illustrate that the non-siloxane Cl₃ CH has no promotional effect.

Comparative Example N

Reaction of Et₃ SiH with methallyl chloride promoted by SnCl₂.

A solution of 0.43 g SnCl₂.2H₂ O in 5.0 g of Pt catalyst solution was prepared. A 50 ml apparatus was charged with 10.5 g (0.09 mol) of Et₃ SiH and 9.2 g (0.09 mol) of methallyl chloride, and the contents heated to 62° C. The Pt/Sn solution (0.05 ml) was added, and heat applied to reflux (83° C.) over 3 hr 40 min. VPC analysis showed no enhancement of Et₃ SiCH₂ CHMeCH₂ Cl yield, indicating that the H₂ PtCl₆ /SnCl₂ couple as disclosed in prior art (U.S. Pat. No. 4,089,882) is an ineffective hydrosilation catalyst for this reaction.

Example 12

Reaction of Et₃ SiH with methallyl chloride promoted by F₃ SiH.

Gaseous F₃ SiH was generated by adding Cl₃ SiH to φSiF₃ containing Bu₃ N and the F₃ SiH so generated was bubbled through a reaction mixture of 11.6 g (0.1 mol) of Et₃ SiH, 9.1 g (0.1 mol) of methallyl chloride, and 0.02 ml Pt catalyst solution for 20 min periods at 21°-48° C., with reaction being stirred at room temperature between periods. Analysis by VPC showed 34.6% conversion of reactants to Et₃ SiCH₂ CHMeCH₂ Cl with a Et₃ SiCH₂ CHMeCH₂ Cl/Et₃ SiCl ratio of 24 on a weight basis. This example shows that F₃ SiH does promote the reaction of Et₃ SiH with methallyl chloride, but not as effectively as Cl₃ SiH. F₃ SiH has the disadvantage of being a gas at room temperature, and is considered to be unstable.

Example 13

Reaction of Et₃ SiH with methallyl chloride promoted by Br₃ SiH.

In a 50 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 9.1 g (0.1 mol) of methallyl chloride, and 2.6 g (0.011 mol) of Br₃ SiH. Pt catalyst solution was added (0.02 ml) at 60° C., followed by heating up to 70° C. over 100 min. Analysis by VPC showed 66.3% conversion of reactants to Et₃ SiCH₂ CHMeCH₂ Cl, indicating that Br₃ SiH also promotes the reaction between Et₃ SiH and methallyl chloride, but not as effectively as Cl₃ SiH. Br₃ SiH has the disadvantage of being pyrophoric.

Comparative Example O

Reaction of Et₃ SiH with methallyl chloride promoted by Cl₃ GeH.

In a 50 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 9.1 g (0.1 mol) of methallyl chloride, and 0.05 ml of Pt catalyst solution. Cl₃ GeH (0.18 g, 0.001 mol) was added at 23° C., with an additional 0.09 g being added 19 min later. Reaction was heated to 68° C. over 51 min and allowed to stand overnight at room temperature. Analysis by VPC showed no formation to Et₃ SiCH₂ CHMeCH₂ Cl indicating that Cl₃ GeH is not an effective promoter for the reaction of Et₃ SiH with methallyl chloride.

Comparative Example P

Reaction of Et₃ SiH with methallyl chloride promoted by PCl₃.

The reaction of Comparative Example O was repeated, except that in one case, 1.4 g of PCl₃ was used instead of Cl₃ GeH, and in the other case, 0.05 ml PCl₃ was precombined with the 0.05 ml Pt catalyst solution. In neither case was there any formation of Et₃ SiCH₂ CHMeCH₂ Cl even after heating several hours, indicating PCl₃ is not an effective promoter for the reaction between Et₃ SiH and methallyl chloride.

                                      TABLE IV                                     __________________________________________________________________________     PROMOTIONAL EFFECTS OF OTHER PROMOTERS                                         Example                                                                             REACTANT A                                                                              OLEFIN   PROMOTER                                                                              YIELD %                                                                              TIME                                       __________________________________________________________________________     Comp. J                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                             --    18.7  3000                                                                              min                                     Comp. N                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            SnCl.sub.2 *                                                                          =18.00                                                                               220                                                                               min                                     12   Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            F.sub.3 SiH**                                                                         34.6  60 min                                     13   Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            Br.sub.3 SiH***                                                                       66.3  100                                                                               min                                     Comp. O                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            Cl.sub.3 GeH                                                                          --    51 min                                     Comp. P                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            PCl.sub.3                                                                             --    7120                                                                              min                                     __________________________________________________________________________      *The Promoter was prepared as a 0.05 ml Pt/Sn solution when a solution of      0.43 g SnCl.sub.2 and 2H.sub.2 O in 5.0 g of Pt catalyst solution were         combined.                                                                      **Although some promotion is seen, F.sub.3 SiH has the disadvantage of         being a gas at room temperature and is considered to be unstable.              ***Br.sub.3 SiH has the disadvantage of being pyrophoric                 

Table IV is to illustrate that the second silane really is the key to the invention since comparative experiments involving other promoters either do not function or have other serious problems associated with them.

Comparative Example Q

Reaction of Cl₃ SiH with methallyl chloride.

In a 50 ml apparatus, there were combined 13.6 g (0.1 mol) of Cl₃ SiH and 9.1 g (0.1 mol) of methallyl chloride, followed by 0.05 ml Pt catalyst solution. Reaction was heated to reflux (44° C.) in 55 min, and was heated at reflux temp. which increased to 84° C. after 6 hr, followed by standing at room temp. overnight. VPC analysis indicated 67.3% conversion of reactants to a single product, Cl₃ SiCH₂ CHMeCH₂ Cl. This example shows that the unpromoted reaction of Cl₃ SiH with methallyl chloride is relatively slow.

Example 14

Reaction of Cl₃ SiH with methallyl chloride promoted by Et₃ SiH.

The reaction of Comparative Example Q was repeated except that 0.08 g (0.5 mol-%) of Et₃ SiH was added after the Pt catalyst. The reaction was heated intermittently up to 100° C. over 170 min, followed by vacuum distillation, which yielded 19.73 g (87.3%) of Cl₃ SiCH₂ CHMeCH₂ Cl. This example shows that low levels of Et₃ SiH effectively promote the reaction between Cl₃ SiH and methallyl chloride.

Comparative Example R

Reaction of equimolar mixture of Cl₃ SiH/MeSiHCl₂ with methallyl chloride.

In a 100 ml apparatus, there as combined 13.6 g (0.1 mol) of Cl₃ SiH, 9.1 g (0.1 mol) of methallyl chloride, and 11.5 g (0.1 mol) of MeSiHCl₂, followed by 0.05 ml Pt catalyst solution at 21° C. Gentle heating caused an exothermic reaction to 52° C. in 22 min. The complete reaction was vacuum distilled, yielding 14.14 g (68.8%) of MeSiCl₂ CH₂ CHMeCH₂ Cl and 4.86 g (21.5%) of Cl₃ SiCH₂ CHMeCH₂ Cl. This example indicates that at the equimolar level, neither Cl₃ SiH nor MeSiHCl₂ is an effective promoter for reactions of the other with methallyl chloride.

Comparative Example S

Reaction of equimolar mixture of Cl₃ SiH/Me₂ SiHCl with methallyl chloride.

In a 50 ml apparatus, there was combined 7.1 g (0.075 mol) of Me₂ SiHCl, 10.2 g (0.075 mol) of Cl₃ SiH, and 6.8 g (0.075 mol) of methallyl chloride. Pt catalyst solution (0.02 ml) was added at 31° C. causing a violent exothermic reaction to more than 60° C. in 3 min. VPC analysis of the complete reaction showed 73.5% conversion to Me₂ SiClCH₂ CHMeCH₂ Cl and 2.9% conversion to Cl₃ SiCH₂ CHMeCH₂ Cl. This example shows that Cl₃ SiH is an effective promoter for the reaction of Me₂ SiHCl with methallyl chloride, and suggests that lower levels of Cl₃ SiH would be just as effective.

                                      TABLE V                                      __________________________________________________________________________     PROMOTION OF Cl.sub.3 SiH AND METHALLYL CHLORIDE                               Example                                                                             REACTANT A                                                                              OLEFIN   PROMOTER YIELD %                                                                              TIME                                     __________________________________________________________________________     Comp. Q                                                                             Cl.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                             --      67.3  360                                                                               min                                   14   Cl.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 CL                                                            0.5 mol % Et.sub.3 SiH                                                                  87.3  170                                                                               min                                   Comp. R                                                                             Cl.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. MeSiHCl.sub.2                                                                      21.5**                                                                               22 min                                   Comp. S                                                                             Cl.sub.3 SiH                                                                            CH.sub.2 ═CMeCH.sub.2 Cl                                                            EqM. Me.sub.2 SiHCl                                                                     2.9**                                          __________________________________________________________________________      **Here, 68.8% MeSiCl.sub.2 CH.sub.2 CHMeCH.sub.2 Cl are produced showing,      if anything, Cl.sub.3 SiH slightly promotes MeSiHCl.sub.2 rather than the      other way around. With regard to Me.sub.2 SiHCl, 73.5% conversion to           Me.sub.2 SiClCH.sub.2 CHM eCH.sub.2 Cl is effected showing Cl.sub.3 SiH i      a good promoter for this reactant as well.                               

Table V shows that promotional effects depend on the nature of the reactant and promoter. If the promoter itself can compete with the reactant to react with the olefin, the reactant may in effect be acting as nothing more than a promoter itself as is seen in Comparative Examples R and S.

Comparative Example T

Reaction of MeSiHCl₂ with methallyl chloride.

In a 50 ml apparatus, there were combined 12.2 g (0.106 mol) of MeSiHCl₂ and 9.6 g (0.106 mol) of methallyl chloride, followed by 0.05 ml Pt catalyst solution at 21° C. Gentle heating caused a smooth exothermic reaction to 120° in 18 min. VPC analysis showed 97.7% conversion to MeSiCl₂ CH₂ CHMeCH₂ Cl. This example shows that the unpromoted reaction of MeSiHCl₂ with methallyl chloride is relatively rapid, and the yield high.

Comparative Example U

Reaction of Me₂ SiHCl with methallyl chloride.

In a 100 ml apparatus, there were combined 14.2 g (0.15 mol) of Me₂ SiHCl and 13.6 g (0.15 mol) of methallyl chloride, followed by 0.05 ml Pt catalyst solution at 21° C. Gentle heating caused a smooth exothermic reaction to 90° C. in 16 in. Reaction was heated at 80° C. until completed (50 min). Vacuum distillation yielded 23.14 g (83.4%) of Me₂ SiClCH₂ CHMeCH₂ Cl.

Comparative Example V

Reaction of equimolar mixture of equimolar mixture of MeSiHCl₂ /Me₂ SiHCl with methallyl chloride.

In a 100 ml apparatus, there were combined 8.6 g (0.75 mol) of MeSiHCl₂, 7.1 g (0.075 mol) of Me₂ SiHCl, and 6.8 g (0.075 mol) of methallyl chloride. Pt catalyst solution (0.01 ml) was added at 32° causing an exothermic reaction to 57° C. and completion in 10 min. Distillation yielded 54.0% of Me₂ SiClCH₂ CHMeCH₂ Cl and 19.6% of MeSiCl₂ CH₂ CHMeCH₂ Cl, indicating that at the equimolar level, neither MeSiHCl₂ nor Me₂ SiHCl is a very effective promoter for reactions of the other with methallyl chloride, in terms of yield, but that reaction rates are increased.

                                      TABLE VI                                     __________________________________________________________________________     PROMOTION OF MeSiHCl.sub.2 AND Me.sub.2 SiHCl AND METHALLYL CHLORIDE           Example                                                                             REACTANT A                                                                              OLEFIN   PROMOTER                                                                              YIELD %                                                                              TIME                                       __________________________________________________________________________     Comp. T                                                                             MeSiHCl.sub.2                                                                           CH.sub.2 ═CMeCH.sub.2 Cl                                                            --     97.7* 18                                                                               min                                      Comp. U                                                                             Me.sub.2 SiHCl                                                                          CH.sub.2 ═CMeCH.sub.2 Cl                                                            --     83.4* 50                                                                               min                                      __________________________________________________________________________      *As already suggested from some of the other examples (e.g., Comparative       examples L, M, R and S), both these reactants react relatively well with       methallyl chloride even without promotion. Neither, however, is a very         effective promoter for the other (see Comparative Example V).            

Comparative Example W

Reaction of Et₃ SiH with methallyl chloride promoted by Cl₃ SiH using other noble metal catalysts.

A standard solution of 69.8 g (0.6 mol) of Et₃ SiH, 54.3 g (0.6 mol) of methallyl chloride, and 8.1 g (0.6 mol) of Cl₃ SiH was made up to simulate the stoichiometry of Example 9. Other noble metal hydrosilation catalyst including platinum acetylacetonate, ethylene platinous chloride, platinum on carbon, bis(triphenylphosphine) platinum dichloride, ruthenium acetylacetonate, dichlorodicarbonyl-bis(triphenylphosphine) ruthenium, rhodium dicarbonyl dichloride dimer, and chloroiridic acid hexahydrate were tested at appropriate concentrations in aliquots of the standard solution. Only ethylene platinous chloride was as effective as the standard H₂ PtCl₆ catalyst solution, with none being more effective. This example indicates that only soluble Pt compounds not containing strongly bound ligands such as acetylacetonate or phosphine groups are effective catalysts in the processes of the present invention. Note, in particular, that platinum on carbon (Pt/C) was ineffective at the lower temperatures (ambient or sub-ambient) where H₂ PtCl₆ is effective, differentiating the instant invention from the prior art. The compounds (CH₂ Pφ₂)₂ PtClSiMe₃, (CH₂ Pφ₂)₂ Pt(SiMe₃)₂ and and [CH₂ (Pφ₂)₂ PtCl]₂ were also ineffective as catalysts in the above standard reaction.

Comparative Example X

Reaction of D₃ D' with allyl chloride; reactants combined at start.

In a 100 ml flask there were combined 62.0 g of 90% D₃ D' (containing 0.2 mol of D₃ D'), 17.0 g (0.22 mol) of allyl chloride, and 0.2 ml of the catalyst used in Comparative Example A. Heat was applied to reflux temperature which increased gradually from 68° C. to 125° C. over 1.5 hrs. The reaction mixture was suction filtered into a 100 ml distillation flask and distilled, yielding the following products:

    ______________________________________                                                        Boiling                                                                        Point/                                                          Product        Pressure    g      Yield                                        ______________________________________                                         D.sub.3 D'Cl   33°/0.3 mm                                                                          37.8   59.7%                                        D.sub.3 D'CH.sub.2 CH.sub.2 CH.sub.3                                                          44°/0.3 mm                                                                          4.0    6.2%                                         D.sub.3 D'CH.sub.2 CH.sub.2 CH.sub.2 Cl*                                                      63°/0.2 mm                                                                          8.0    11.2%                                        D.sub.3 D'CH.sub.2 CH.sub.2 CH.sub.2 D'D.sub.3                                                117°/0.25 mm                                                                        2.4    --                                           ______________________________________                                          *The yield of the desired hydrosilation product was only 11.2%           

Comparative Example Y

Reaction of D₃ D' with allyl chloride; olefin added to hydrosiloxane.

In the apparatus of Comparative Example X, there were placed 56.4 g (0.2 mol) of D₃ D' which was heated to 78° C., when 0.2 ml of the catalyst used in Example 2 was added. Dropwise addition of 15.3 g (0.2 mol) of allyl chloride was begun and the reaction temperature was maintained at 95°-124° C. until completion (37 mins). The reaction mixture was distilled yielding the following products:

    ______________________________________                                                         Boiling                                                                        Point/                                                         Product         Pressure    g      Yield                                       ______________________________________                                         D.sub.3 D'Cl    27°/0.7 mm                                                                          22.0   34.8%                                       D.sub.3 D'CH.sub.2 CH.sub.2 CH.sub.3                                                           29°/0.7 mm                                                                          16.6   33.0%                                       D.sub.3 D'CH.sub.2 CH.sub.2 Cl*                                                                53°/0.2 mm                                                                          13.9   19.4%                                       D.sub.3 D'CH.sub.2 CH.sub.2 CH.sub.2 D'D.sub.3                                                 --          trace  --                                          Heavies         --           1.6   --                                          ______________________________________                                          *The yield of the desired hydrosilation product was 19.4%, a 73.2%             relative improvement over the 11.2% obtained in Comparative Example G.   

Example 15

Reaction of equimolar mixture of D₃ D'/Cl₃ SiH with allyl chloride.

In a 100 ml apparatus, there were combined 15.5 g (0.114 mol) of Cl₃ SiH, 32.3 g (0.114 mol) of D₃ D' and 8.8 g (0.114 mol) of allyl chloride. Pt catalyst solution (0.05 ml) was added at 21° C., causing a gentle exothermic reaction to 83° C. in 52 min. Vacuum distillation yielded 7.02 g (29.0%) of Cl₃ SiCH₂ CH₂ CH₂ Cl and 10.2 g (24.9%) of D₃ CH₂ CH₂ CH₂ Cl. This example shows that Cl₃ SiH at the equimolar level increases both rate and yield of the reaction between D₃ D' and allyl chloride.

Example 16

Reaction of equimolar mixture of D₃ D'/MeSiHCl₂ with allyl chloride.

In a 100 ml apparatus, there were combined 15.8 g (0.14 mol) of MeSiHCl₂, 38.6 g (0.14 mol) of D₃ D', and 10.5 g (0.1 mol) of allyl chloride. Pt catalyst solution (0.05 ml) was added at 19° C. and the reaction mixture allowed to stir overnight at 28° C. (heat generated by magnetic stirrer). Gentle heat was applied to the unreacted mixture, causing an exothermic reaction to 95° C. in 45 min. Vacuum distillation yielded 5.82 g (22.2%) of MeSiCl₂ CH₂ CH₂ CH₂ Cl and 15.65 g (31.8% of D₃ D'CH₂ CH₂ CH₂ Cl, indicating that at the equimolar level, MeSiHCl₂ is more effective than Cl₃ SiH at increasing the yield of the reaction between D₃ D' and allyl chloride.

Comparative Example Z

Reaction of equimolar mixture of D₃ D'/MeSiHCl₂ with allyl chloride in the presence of tributylamine.

The reaction of Example 16 was repeated except at 0.1 mol of each reactant was used and 0.05 ml of Bu₃ N was added after the Pt catalyst. The reaction exothermed from 22° C. to 48° C. in 108 min, and was vacuum distilled, yielding 10.09 g (52.7%) of MeSiCl₂ CH₂ CH₂ CH₂ Cl and 0.8 g (2.2%) of D₃ D'CH₂ CH₂ CH₂ Cl. The tertiary amine promoter (Bu₃ N is claimed as a promoter for MeSiHCl₂ in its reaction with allyl chloride) enhances the hydrochlorosilane reactivity, and interferes with the hydrochlorosilane promotion of the hydrosiloxane reactivity. Note that the relative reactivities of D₃ D' and MeSiHCl₂ are reversed in Examples 16 and Comparative Example Z.

Example 17

Reaction of equimolar mixture of D₃ D'/Et₃ SiH with allyl chloride.

In a 100 ml apparatus, there were combined 28.3 g (0.1 mol) of 98% D₃ D', 11.6 g (0.1 mol) of Et₃ SiH, and 7.7 g (0.1 mol of allyl chloride. Pt catalyst solution (0.05 ml) was added at 22° C., followed by heating up to 66° C. over 145 min. Vacuum distillation yielded 7.15 g (19.9%) of D₃ D'CH₂ CH₂ CH₂ Cl, and a trace of Et₃ SiCH₂ CH₂ CH₂ Cl. This example shows that neither D₃ D' nor Et₃ SiH are very effective promoters at the equimolar level for reactions of the other with allyl chloride.

Example 18

Reaction of equimolar mixture of D₃ D'/MD'M with allyl chloride.

In a 100 ml apparatus, there were combined 22.2 g (0.1 mol of MD'M, 30.5 g (0.1 mol) of 92% D₃ D', and 7.7 g (0.1 mol) of allyl chloride. Pt catalyst solution (0.05 ml) was added at 25° C., and heat applied to 80° C. over 40 min, followed by an exothermic reaction to 140° C. over 15 min. Vacuum distillation yielded 1.15 g (3.9%) of M₂ D'CH₂ CH₂ CH₂ Cl and 6.91 g (19.3%) of D₃ D'CH₂ CH₂ CH₂ Cl, indicating that neither D₃ D' nor MD'M are very effective promoters for reaction of the other with allyl chloride when used at the equimolar level.

Example 19

Reaction of equimolar mixture of D₃ D'/Me₂ SiHCl with allyl chloride.

In a 100 ml apparatus, there were combined 30.5 g (0.1 mol) of 92% D₃ ', 9.5 g (0.1 mol) of Me₂ SiHCl, and 7.7 g (0.1 mol) of allyl chloride. Pt catalysts solution (0.05 ml was added at 42° C. and heat applied to 97.5° C. over 144 min. Vacuum distillation yielded 3.99 g (23.3%) of Me₂ SiClCH₂ CH₂ CH₂ Cl and 11.15 g (31.1%) of D₃ D'CH₂ CH₂ CH₂ Cl. This example shows that Me₂ SiHCl is slightly less effective than MeSiHCl₂ in promoting the reaction between D₃ D' and allyl chloride when used at the equimolar level.

                                      TABLE VII                                    __________________________________________________________________________     PROMOTION OF D.sub.3 D' AND ALLYL CHLORIDE                                     Example                                                                             REACTANT A                                                                              OLEFIN   PROMOTER YIELD %                                                                              TIME                                     __________________________________________________________________________     Comp. X                                                                             D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                              --      11*   90 min                                   Comp. Y                                                                             D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                              --      19.4  37 min                                   15   D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Cl.sub.3 SiH                                                                       24.9  52 min                                   16   D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. MeSiHCl.sub.2                                                                      31.8  45 min                                   Comp. Z                                                                             D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. MeSiHCl.sub.2                                                                       2.2  108                                                                               min                                                          and tributylamine                                       17   D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Et.sub.3 SiH                                                                       19.9  145                                                                               min                                   18   D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. MD'M                                                                               19.3  55 min                                   19   D.sub.3 D'                                                                              CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Me.sub.2 SiHCl                                                                     31.1  144                                                                               min                                   __________________________________________________________________________      *When the olefin was later added to the hydrosiloxane rather than at the       start, the yield was improved to 19.4% (see Comparative Example Y).      

Several observations may be made from Table VII. First, Comparative Example Z shows how tributylamine interferes with promotion relative to Example 16.

Second, comparing Table VII to Table I, it can be seen that the yields of the reaction may vary merely by changing the olefin reactant. For example, both MeSiHCl₂ and MeSiHCl are stronger promoters than Cl₃ SiH when using allyl chloride while, when methallyl chloride is used as the reactant olefin (Table I), the opposite is true.

Comparative Example AA

Reactant of MD'M with allyl chloride.

In a 100 ml apparatus, there were combined 22.3 g (0.1 mol) of MD'M and 7.7 g (0.1 mol) of allyl chloride. Pt catalyst solution (0.05 ml) was added at 48° C., causing a gradual exothermic reaction to 120° C. in 41 min. Vacuum distillation yielded 4.50 g (15.1%) of M₂ D'CH₂ CH₂ CH₂ Cl as one of the several products.

Comparative Example BB

Reaction of MD'M with allyl chloride promoted by SnCl₂.

The reaction of Comparative Example AA was repeated except that the Pt/Sn catalyst solution of Comparative Example K was used instead of the standard H₂ PtCl₆ solution. There was an exothermic reaction from 45° C. to 73° C. over 53 min. VPC analysis showed M₂ D'Cl was the major product with only a trace of M₂ D'CH₂ CH₂ CH₂ Cl, such that SnCl₂ does not promote the hydrosilation reaction between MD'M and allyl chloride.

Example 20

Reaction of equimolar mixture of MD'M/Cl₃ SiH with allyl chloride.

In a 100 ml apparatus, there were combined 11.1 g (0.05 mol) of MD'M, 6.8 g (0.05 mol) of Cl₃ SiH, and 3.9 g (0.05 mol) of allyl chloride. Pt catalyst solution (0.025 ml) was added at 23° C., causing a violent exothermic reaction to 96° C. in 3 min. Vacuum distillation yielded 0.13 g of Cl₃ SiCH₂ CH₂ CH₂ Cl and 5.99 g (40.1%) of M₂ D'CH₂ CH₂ CH₂ Cl. This example shows that Cl₃ SiH at the equimolar level is an effective promoter for the reaction of MD'M with allyl chloride, enhancing both rate and yield relative to the unpromoted reaction of Comparative Example AA.

Example 21

Reaction of equimolar mixture of MD'M/MeSiHCl₂ with allyl chloride.

In a 100 ml apparatus, there were combined 16.7 g (0.075 mol) of MD'M, 8.6 g (0.075 mol) of MeSiHCl₂, and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 54° C. and the reaction heated up to 84° C. over 2 hr. Vacuum distillation yielded 44.4% of M₂ D'CH₂ CH₂ CH₂ Cl and 7.6% of MeSiCl₂ CH₂ CH₂ CH₂ Cl. This example shows that MeSiCl₂ H at the equimolar level effectively enhances yield, but not rate, of the reaction between MD'M and allyl chloride.

Comparative Example CC

Reaction of equimolar mixture of MD'M/Me₂ SiHCl with allyl chloride.

In a 100 ml apparatus, there were combined 22.3 g (0.1 mol) of MD'M, 9.5 g (0.1 mol) of Me₂ SiHCl, and 7.7 g (0.1 mol) of allyl chloride. Pt catalyst solution was added at 74° C. (0.05 ml), followed by heating up to 92° C. over 162 min. Vacuum distillation of the reaction yielded 18.1% of M₂ D'CH₂ CH₂ CH₂ Cl and 10.3% of Me₂ SiClCH₂ CH₂ CH₂ Cl. This example shows that neither MD'M nor Me₂ SiHCl is an effective promoter at the equimolar level for reactions of the other with allyl chloride.

Example 22

Reaction of equimolar mixture of MD'M/Et₃ SiH with allyl chloride.

In a 100 ml apparatus, there were combined 11.1 g (0.05 mol) of MD'M, 5.8 g (0.05 mol) of Et₃ SiH, and 3.8 g (0.05 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 54° C. and the reaction heated to 90° C. over 28 min. VPC analysis of the reaction mixture showed 23.9% of M₂ D'CH₂ CH₂ CH₂ Cl and 7.2% Et₃ SiCH₂ CH₂ CH₂ Cl, indicating that both MD'M and Et₃ SiH are slightly effective promoters at the equimolar level for reactions of the other with allyl chloride.

                                      TABLE VIII                                   __________________________________________________________________________     PROMOTION OF MD'M AND ALLYL CHLORIDE                                           Example                                                                              REACTANT A                                                                              OLEFIN   PROMOTER YIELD %                                                                              TIME                                    __________________________________________________________________________     Comp. AA                                                                             MD'M     CH.sub.2 ═CHCH.sub.2 Cl                                                              --      15.1  41 min                                  Comp. BB                                                                             MD'M     CH.sub.2 ═CHCH.sub.2 Cl                                                             Sn.sub.2 Cl.sub.2 *                                                                     --    53 min                                  20    MD'M     CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Cl.sub.3 SiH                                                                       40.1  3  min                                  21    MD'M     CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. MeSiHCl.sub.2                                                                      44.4  120                                                                               min                                  Comp. CC                                                                             MD'M     CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Me.sub.2 SiHCl                                                                      18.1 162                                                                               min                                  22    MD'M     CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Et.sub.3 SiH                                                                       23.9  28 min                                  __________________________________________________________________________      *This was the same Pt/Sn catalyst solution of Comparative Example K.           **Because promotion was just under 20%, this was not included as an            example of the invention.                                                

Again, although Table II varies from Table VIII only by the olefin employed, differences are observed. For example, MeSiHCl₂ promotes greater yield than Cl₃ SiH (although rate is much slower). Both, however, are still greater than Et₃ SiH which in turn is greater than Me₂ SiHCl.

Comparative Example DD

Reaction of Et₃ SiH with allyl chloride.

In a 100 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 7.7 g (0.1 mol of allyl chloride, and 0.05 ml Pt catalyst solution at 19° C. After stirring 1 hr, temperature had increased to 27° C., followed by heating at 70° C. for 17 hr. The incomplete reaction was vacuum distilled, yielding 8.9 g (42%) of Et₃ SiCl, and 3.0 g (15.5%) of Et₃ SiCH₂ CH₂ CH₂ Cl. The Et₃ SiCH₂ CH₂ C₂ Cl/Et₃ SiCl molar selectivity ratio was 0.37. This example shows that the unpromoted reaction between Et₃ SiH and CH₂ =CHCH₂ Cl is very slow.

Comparative Example EE

Reaction of equimolar mixture of Et₃ SiH/Cl₃ SiH with allyl chloride.

In a 50 ml apparatus, there were combined 11.6 g (0.01 mol) of Et₃ SiH, 13.6 g (0.1 mol) of Cl₃ SiH, and 7.7 g (0.01 mol) of allyl chloride. Pt catalyst solution (0.05 ml) was added, causing a gentle exothermic reaction from 19° C. to 36° C. in 35 min. Heat was applied up to 66° C. over the next 75 min. Vacuum distillation yielded 0.80 g (4.2%) of Et₃ SiCH₂ CH₂ CH₂ Cl and 11.48 g (54.2%) of Cl₃ SiCH₂ CH₂ CH₂ Cl. This example shows that Et₃ SiH at the equimolar level is an effective promoter for the reaction between Cl₃ SiH and allyl chloride, since that reaction is very slow at reflux temperature in the absence of a promoter.

Comparative Example FF

Reaction of equimolar mixture of Et₃ SiH/Cl₃ SiH with allyl chloride, latter added to former.

The reaction of Comparative Example EE was repeated except that the allyl chloride was added dropwise to a mixture of the two silanes and the Pt catalyst beginning at 39° C. There was a smooth exothermic reaction up to 80° over the addition (30 min) followed by 15 min at 80° C. Vacuum distillation yielded 3.17 g (16.5%) of Et₃ SiCH₂ CH₂ CH₂ Cl, and 10.67 g (50.3%) of Cl₃ SiCH₂ CH₂ CH₂ Cl. This example shows that adding the olefin as above allows both Cl₃ SiH and Et₃ SiH to promote the hydrosilation reaction rate of the other toward allyl chloride. Selectivity and yield were also improved for Et₃ SiH, with a Et₃ SiCH₂ CH₂ Cl/Et₃ SiCl molar selectivity ratio of 2.5.

Example 23

Reaction of equimolar mixture of Et₃ SiH/Cl₃ SiH with allyl chloride, former added to latter.

The reaction of Comparative Example FF was repeated except that the silane mixture was added dropwise to the allyl chloride containing the Pt catalyst, beginning at 40.5° C. Heat was applied up to 50° C. over 132 min (time of addition). Vacuum distillation yielded 6.30 g (32.7%) of Et₃ SiCH₂ CH₂ CH₂ Cl and 7.71 g (36.4%) of Cl₃ SiCH₂ CH₂ CH₂ Cl. This example shows that while this sequence of combination of reactants causes a lower reaction rate, yield and selectivity of the Et₃ SiH reaction with allyl chloride are improved further. The Et₃ SiCH₂ CH₂ CH₂ Cl/Et₃ SiCl molar ratio was 2.82.

Example 24

Reaction of Et₃ SiH with 10/1 molar mixture of allyl chloride/Cl₃ SiH, latter added to former.

In a 25 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH and 0.05 ml of Pt catalyst solution. Heat was applied to 60° C. and addition of a mixture of 7.7 g (0.1 mol) of allyl chloride and 1.4 g (0.01 mol) of Cl₃ SiH begun. There was a smooth exothermic reaction up to 80° C. by the end of the addition (15 min) with temperature continuing to rise to 129° C. 5 min later. Vacuum distillation yielded 12.12 g (63.0%) of Et₃ SiCH₂ CH₂ CH₂ Cl, with a Et₃ SiCH₂ CH₂ CH₂ Cl/Et₃ SiCl molar ratio of 2.73. This example shows that low levels of Cl₃ SiH effectively promote both rate and yield of the reaction between Et₃ SiH and allyl chloride, particularly when the low levels are maintained throughout the reaction by replenishment.

Example 25

Reaction of 8/1 molar mixture of Et₃ SiH/Cl₃ SiH with allyl chloride, latter added to former.

In a 100 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 1.7 g (0.0125 mol) of Cl₃ SiH and 0.05 ml of Pt catalyst solution. The mixture was heated to 65° C. and addition of 7.7 g (0.1 mol) of allyl chloride begun. There was an exothermic reaction to 108.5° C. over 16 min, followed by a temperature drop. Addition of allyl chloride was complete in 31 min, with heat then applied at reflux (up to 114° C.) over 170 min. Vacuum distillation yielded 7.88 g (40.9%) of Et₃ SiCH₂ CH₂ CH₂ Cl with a Et₃ SiCH₂ CH₂ CH₂ Cl/Et₃ SiCl selectivity ratio of 1.13. This example shows that this sequence of combination of reactants allows the Cl₃ SiH promoter to be consumed, at which point the reaction of Et₃ SiH with allyl chloride proceeds at the low rate and selectivity exhibited in Comparative Example DD.

Example 26

Reaction of 10/1 molar mixture of Et₃ SiH/Cl₃ SiH with allyl chloride, former added to latter.

In a 50 ml apparatus, there were combined 7.7 g (0.1 mol) of allyl chloride and 0.05 ml of Pt catalyst solution. the mixture was heated to 44° C. and addition of a mixture of 11.6 g (0.1 mol) of Et₃ SiH and 1.4 g (0.01 mol) of Cl₃ SiH begun. Reaction was heated up to 54.5° C. during addition (30 min). There was a violent exothermic reaction from 62° C. to 110° C. 16 min later. Vacuum distillation yielded 7.79 g (40.5%) of Et₃ SiCH₂ CH₂ CH₂ Cl, with a Et₃ SiCH₂ CH₂ CH₂ Cl/Et₃ SiCl selectivity ratio of 1.23. This example and the previous one show that the preferred sequence of combination of reactants for most effective Cl₃ SiH promotion of the reaction of Et₃ SiH with allyl chloride is that of Example 24.

Example 27

Reaction of Et₃ SiH with allyl chloride using Cl₃ SiH/H₂ PtCl₆ solution as catalyst.

The reaction of Comparative Example DD was repeated except that 0.1 ml of the Cl₃ SiH/H₂ PtCl₆ catalyst solution of Example 16 was used instead of the standard H₂ PtCl₆ solution. Heat was applied over 205 min up to 90° C., followed by vacuum distillation which yielded 4.36 g (22.6%) Et₃ SiCH₂ CH₂ CH₂ Cl, with a Et₃ SiCH₂ CH₂ CH₂ Cl/Et₃ SiCl ratio of 0.35. This example shows that very low levels of Cl₃ SiH cause modest rate increases in the reaction between Et₃ SiH and allyl chloride, but do not affect selectivity.

                                      TABLE IX                                     __________________________________________________________________________     PROMOTION OF Et.sub.3 SiH AND ALLYL CHLORIDE                                   Example                                                                              REACTANT A                                                                              OLEFIN   PROMOTER    YIELD %                                                                              TIME                                 __________________________________________________________________________     Comp. DD                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                              --         15.5  1000                                                                              min                               Comp. EE                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Cl.sub.3 SiH*                                                                          4.2  110                                                                               min                               Comp. FF                                                                             Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Cl.sub.3 SiH                                                                          16.5  45 min                               23    Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Cl.sub.3 SiH                                                                          32.7  132                                                                               min                               24    Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             10/1 Olefin/Cl.sub.3 SiH                                                                   63.0  20 min                               25    Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             13 mol. % Cl.sub.3 SiH                                                                     40.9  170                                                                               min                               26    Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             10 mol. % Cl.sub.3 SiH                                                                     40.5  46 min                               27    Et.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             0.1 ml Cl.sub.3 Si/H.sub.2 PtCl.sub.6 **                                                   22.6  205                                                                               min                               __________________________________________________________________________      *Compare to Example 8 where, though only difference is in the olefin, the      yield was 82.5%.                                                               **When 0.1 ml (i.e. very small quantity of Cl.sub.3 SiH) of catalyst           solution of Example 16 is used, modest increases are found again               indicating the difference when only the olefin is charged.               

Table IX again illustrates a number of interesting observations. First, in comparing Examples FF and 23 to Example EE, the only difference is in the order the reactants are combined. After the olefin to a mixture of Et₃ SiH and Cl₃ SiH promoter later rather than at the start increased the yield to 16.5% while, when Et₃ SiH and Cl₃ SiH were precombined and added to the olefin later, the yield rose to 32.7%.

Similarly, the order of combination effects lower yields in Examples 25 and 26 compared to Example 24. In Example 24, the olefin and Cl₃ SiH are given a chance to precombine before being added to Et₃ SiH. By contrast, both the Cl₃ SiH and Et₃ SiH are precombined in Examples 25 and 26 whether they are added to the olefin (Example 26) or the olefin is later added to them (Example 25).

Finally, comparing Examples EE and 27 to Example 8 in Table III, it can be observed once more that yields may be greatly affected merely by changing the olefin of the reaction.

Comparative Example GG

Reaction of Me₂ SiHCl with allyl chloride.

In a 100 ml apparatus, there were combined 18.9 g (0.2 mol) of Me₂ SiHCl, 15.3 g (0.2 mol) of allyl chloride, and 0.05 ml Pt catalyst solution at 18.5° C., followed by heating at reflux for 50 hr. An equivalent quantity of Pt catalyst solution was added during the reflux period. Vacuum distillation of the incomplete reaction yielded 12.6% of Me₂ SiClCH₂ CH₂ CH₂ Cl. This example shows that the unpromoted reaction of Me₂ SiHCl with allyl chloride proceeds very slowly at reflux temperature.

Example 28

Reaction of equimolar mixture of Et₃ SiH/Me₂ SiHCl with allyl chloride.

In a 100 ml apparatus, there were combined 7.1 g (0.075 mol) of Me₂ SiHCl, 8.7 g (0.075 mol) of Et₃ SiH and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution was added (0.05 ml) at 34° C. Gentle heating caused a smooth exothermic reaction to 92° over 36 min. Vacuum distillation yielded 42.5% of Me₂ SiClCH₂ CH₂ CH₂ Cl and 4.8% of Et₃ SiCH₂ CH₂ CH₂ Cl. This example shows that Et₃ SiH at the equimolar level is an effective promoter for the reaction between Me₂ SiHCl and allyl chloride.

Example 29

Reaction of equimolar mixture of Et₃ SiH/MeSiHCl₂ with allyl chloride.

In a 100 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 11.5 g (0.1 mol) of MeSiHCl₂, and 7.7 g (0.1 mol) of allyl chloride. Pt catalyst solution (0.05 ml) was added at 21° C., gentle heating caused an exothermic reaction to 88° C. over 150 min. Vacuum distillation yielded 40.4% of MeSiCl₂ CH₂ CH₂ CH₂ Cl and 13.0% of Et₃ SiCH₂ CH₂ CH₂ CH₂ Cl. This example shows that both MeSiHCl₂ and Et₃ SiH are promoters at the equimolar level for reactions of the other with allyl chloride. The promotion effects are milder than those between Et₃ SiH and Cl₃ SiH as shown in Comparative Example FF. The unpromoted reaction between MeSiHCl₂ and allyl chloride is known to be slow at reflux.

Comparative Example HH

Reaction of equimolar mixture of Cl₃ SiH/MeSiHCl₂ with allyl chloride.

In a 50 ml apparatus, there were combined 13.1 g (0.097 mol) of Cl₃ SiH, 11.1 g (0.097 mol) of MeSiHCl₂, and 7.4 g (0.097 mol) of allyl chloride. Pt catalyst solution (0.05 ml) was added at 21.5° C., causing a smooth exothermic reaction to 55° C. over 42 min, followed by heating at reflux (up to 67° C.) over 330 min. Vacuum distillation yielded 12.14 g of a mixture of Cl₃ SiCH₂ CH₂ CH₂ Cl/MeSiCl₂ CH₂ CH₂ CH₂ Cl in a 2.04/1 ratio. This example shows that neither Cl₃ SiH nor MeSiHCl₂ is a very effective promoter at the equimolar level for reactions of the other with allyl chloride.

Comparative Example II

Reaction of equimolar mixture of Cl₃ SiH/Me₂ SiHCl with allyl chloride.

In a 100 ml apparatus, there were combined 7.1 g (0.075 mol) of Me₂ SiHCl, 10.2 g (0.075 mol) of Cl₃ SiH, and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 33° C., causing an exothermic reaction to 47° C. in 7 min. VPC analysis 14 min. later showed a complete reaction. Vacuum distillation yielded 60.4% Cl₃ SiCH₂ CH₂ CH₂ Cl and 8.6% Me₂ SiClCH₂ CH₂ CH₂ Cl. This example shows that Me₂ SiHCl is an effective promoter for the reaction of Cl₃ SiH with allyl chloride at the equimolar level.

Example 30

Reaction of equimolar mixture of MeSiHCl₂ /Me₂ SiHCl with allyl chloride.

In a 100 ml apparatus, there were combined 8.6 g (0.075 mol) of MeSiHCl₂, 7.1 g (0.075 mol) of Me₂ SiHCl, and 5.7 g (0.075 mol) of allyl chloride. Pt catalyst solution (0.01 ml) was added at 37° C., followed by heating up to 45° C. over 1 hr. Vacuum distillation yielded 31.3% of MeSiCl₂ CH₂ CH₂ CH₂ Cl and 22.6% of Me₂ SiClCH₂ CH₂ CH₂ Cl. This example shows that neither Me₂ SiHCl nor MeSiHCl₂ is a very effective promoter at the equimolar level for reactions of the other with allyl chloride.

                                      TABLE X                                      __________________________________________________________________________     PROMOTION OF Me.sub.2 SiHCl AND ALLYL CHLORIDE                                 Example                                                                              REACTANT A                                                                              OLEFIN   PROMOTER YIELD %                                                                              TIME                                    __________________________________________________________________________     Comp. GG                                                                             Me.sub.2 SiHCl                                                                          CH.sub.2 ═CHCH.sub.2 Cl                                                              --      12.6  3000                                                                              min                                  28    Me.sub.2 SiHCl                                                                          CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Et.sub.3 SiH*                                                                      42.5* 36 min                                  Comp. II                                                                             Me.sub.2 SiHCl                                                                          CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. Cl.sub.3 SiH                                                                       8.6   7  min                                  30    Me.sub.2 SiHCl                                                                          CH.sub.2 ═CHCH.sub.2 Cl                                                             EqM. MeSiHCl.sub.2                                                                      22.6  >60                                                                               min                                  __________________________________________________________________________      *Compare to Comparative Example M. Here the production from the                corresponding olefin was 81.1%.                                          

This Table shows again how varying the olefin and reactant also changes the yields. For example, the same quantity of Et₃ SiH and Me₂ SiHCl(Comparative Example M versus Example 28) promotes 81.1% yield with methallyl chloride and only 42.5% yield with allyl chloride.

Comparative Example JJ

Reaction of Cl₃ SiH with allyl chloride, former added to latter.

In a 50 ml apparatus, there were combined 7.7 g (0.1 mol) of allyl chloride and 0.05 ml Pt catalyst solution. The mixture was heated to reflux (43° C.) and the addition of 13.6 g (0.1 mol) of Cl₃ SiH begun. Addition was complete in 33 min, during which the reflux temp. had increased to 47° C. After another 16 min, reflux temp. was 70° C. and reaction was complete. Vacuum distillation yielded 14.01 g (66.1%) of Cl₃ SiCH₂ CH₂ CH₂ Cl. This example shows that the reaction between Cl₃ SiH and allyl chloride, which is slow at the reflux temperature of the combined reactants, can be accelerated by beginning at the higher reflux temperature of the allyl chloride.

Comparative Example KK

Reaction of Cl₃ SiH with allyl chloride promoted by Cl₃ GeH.

The reaction of Comparative Example JJ was repeated except that all reactants and catalyst were combined at the start and 0.18 g of Cl₃ GeH added at once (instead of Et₃ SiH). VPC analysis showed no promotion of the reaction between Cl₃ SiH and allyl chloride even after heating at reflux for 3 hr. Cl₃ GeH is not an effective promoter for the reaction between Cl₃ SiH and allyl chloride under these conditions.

Example 31

Reactant of 10/1 molar mixture of Cl₃ SiH/Et₃ SiH with allyl chloride, former added to latter.

In a 50 ml apparatus, there were combined 7.7 g (0.1 mol) of allyl chloride and 0.05 ml of Pt catalyst solution. At 42° C., addition of a mixture of 13.6 g (0.1 mol) of Cl₃ SiH and 1.2 g (0.01 mol) of Et₃ SiH was begun. There was an exothermic reaction during addition (27 min) to 77° C. Vacuum distillation yielded 13.98 g (65.9%) of Cl₃ SiCH₂ CH₂ CH₂ Cl. This example shows that Et₃ SiH is an effective promoter for the reaction between Cl₃ SiH and allyl chloride, increasing the reaction rate, but not the yield or selectivity.

Example 32

Reaction of 15/1 molar mixture of Cl₃ SiH/Et₃ SiH with allyl chloride, latter added to former.

In a 50 ml apparatus, there were combined 12.0 g (0.09 mol) of Cl₃ SiH, 0.7 g (0.006 mol) of Et₃ SiH, and 0.04 ml of Pt catalyst solution. The addition of 6.8 g (0.09 mol) of allyl chloride was begun at 24° C. causing an exothermic reaction to 63° C. during addition (18 min). Vacuum distillation yielded 11.92 g (63.2%) of Cl₃ SiCH₂ CH₂ CH₂ Cl, showing that Et₃ SiH promotes the reaction between Cl₃ SiH and allyl chloride at lower temperatures than phenothiazine, such that no external heating is required. This example also shows that the reactant combination sequence has little effect effect on yield or selectivity of the reaction between Cl₃ SiH and allyl chloride.

Example 33

Reaction between Cl₃ SiH and allyl chloride promoted by Et₃ SiH.

To a mixture of 13.6 g (0.1 mol) of Cl₃ SiH and 0.05 ml Pt catalyst solution in a 50 ml apparatus, there was added dropwise 7.7 g (0.1 mol) of allyl chloride at 24° C. VPC analysis 1 hr. after start of addition (30 min. after completion of addition) showed less than 1% conversion of reactants to products. Et₃ SiH (0.04 ml) was added, causing a smooth exothermic reaction to 67° C. in 24 min. Vacuum distillation yielded 14.29 g (67.4%) of Cl₃ SiCH₂ CH₂ CH₂ Cl. This example shows that the reaction between Cl₃ SiH and allyl chloride is promoted very effectively in rate by very low levels (0.33 mol.%) of Et₃ SiH, with the elimination of external heating.

                                      TABLE XI                                     __________________________________________________________________________     PROMOTION OF Cl.sub.3 SiH AND ALLYL CHLORIDE                                   Example                                                                              REACTANT A                                                                              OLEFIN   PROMOTER  YIELD %                                                                              TIME                                   __________________________________________________________________________     Comp. JJ                                                                             Cl.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                              --       66.1  49 min                                 Comp. KK                                                                             Cl.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             Cl.sub.3 GeH                                                                             No    7180                                                                              min                                                                   Promotion                                    31    Cl.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             10/1 Cl.sub.3 SiH/Et.sub.3 SiH                                                           65.9* 27 min                                 32    Cl.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             15/1 Cl.sub.3 SiH/Et.sub.3 SiH                                                           63.2**                                                                               18 min                                 33    CH.sub.3 SiH                                                                            CH.sub.2 ═CHCH.sub.2 Cl                                                             0.33 mol. % Et.sub.3 SiH                                                                  67.4***                                                                             24 min                                 __________________________________________________________________________      *With Et.sub.3 SiH acting as promoter (similar to Example 26 but the rati      of Cl.sub.3 SiH and Et.sub.3 SiH is reversed), rate is increased but yiel      is not increased; here the mixture is added to olefin.                         **Here, the order of reaction was reversed (olefin added to mixture) with      again higher rates but no effect on yield.                               

This Table XI shows that Cl₃ SiH and allyl chloride can be promoted primarily in their rate by both Et₃ SiH and EtMe₂ SiH and slightly in yield by EtMe₂ SiH. Very small quantities of Et₃ SiH may be used to promote rate (Example 33), and the order of mixing does not seem to matter (Contrast to Comparative Examples EE and FF and Examples 23-26 as discussed in Table IX.)

Comparative Example OO

Reaction of Et₃ SiH with 3-chloro-1-butene.

In a 50 ml apparatus, there were combined 4.5 g (0.039 mol) of Et₃ SiH and 3.5 g (0.039 mol) of 3-chloro-1-butene. Pt catalyst solution (0.01 ml) was added at 22° C., followed by heating up to 77° C. over 70 min. Vacuum distillation yielded 3.46 g (58.9%) of Et₃ SiCl and 0.61 g (7.6%) of Et₃ SiCH₂ CH₂ CHMeCl. This example demonstrates the low yield of Et₃ SiCH₂ CH₂ CHMeCl from the unpromoted reaction of Et₃ SiH with 3-chloro-1-butene.

EXAMPLE 34

Reaction of Et₃ SiH with 3-chloro-1-butene promoted by Cl₃ SiH.

The reaction of Comparative Example 00 was repeated except that 1.0 g (0.007 mol) of Cl₃ SiH was also added. There was a smooth exothermic reaction to 55° C. in 52 min. with no external heating. Vacuum distillation yielded 2.54 g (22.5%) of Et₃ SiCl and 11.40 g (73.6%) of Et₃ SiCH₂ CH₂ CHMeCl. This example shows that Cl₃ SiH is a very effective promoter for the reaction between Et₃ SiH and 3-chloro-1-butene, increasing both rate and yield, and eliminating external heating.

Comparative Example PP

Reaction of Et₃ SiH with 4-methyl-1-pentene.

In a 50 ml apparatus, there were combined 6.3 g (0.075 mol) of 4-methyl-1-pentene, 8.7 g (0.075 mol) of Et₃ SiH, and 0.01 ml of Pt catalyst solution at 22° C. Heat was applied over 2 hr. up to 58° C., with VPC analysis showing 11.0% conversion of reactants to Et₃ SiCH₂ CH₂ CHMe₂. This example demonstrates the low rate of the unpromoted reaction between Et₃ SiH and 4-methyl-1-pentene.

Example 35

Reaction of Et₃ SiH with 4-methyl-1-pentene promoted by Cl₃ SiH.

The reaction of Comparative Example PP was repeated except that Cl₃ SiH (1.0 g, 0.0075 mol) was also added. There was a rapid exothermic reaction from 23° C. to 70° C. in 8 min. VPC analysis at that point showed 29.7% conversion of reactants to Et₃ SiCH₂ CH₂ CH₂ CHMe₂, demonstrating that Cl₃ SiH is an effective promoter for the reaction of Et₃ SiH with 4-methyl-1-pentene.

Comparative Example QQ

Reaction of equimolar mixture of Et₃ SiH/MeSiHCl₂ with 4-methyl-1-pentene.

In a 50 ml apparatus, there were combined 8.1 g (0.07 mol) of Et₃ SiH, 8.1 g (0.07 mol) of MeSiHCl₂, and 5.9 g (0.07 mol) of 4-methyl-1-pentene. Pt catalyst solution (0.05 ml) was added at 21° C. Gentle heating caused and exothermic reaction to 55° C. in 38 min. VPC analysis of the complete reaction 90 min. later showed a mixture of MeSiCl₂ CH₂ CH₂ CH₂ CHMe₂ /Et₃ SiCH₂ CH₂ CH₂ CHMe₂ in a molar ratio of 3.3/1. This example shows that neither MeSiHCl₂ nor Et₃ SiH is a very effective promoter at the equimolar level for reactions of the other with 4-methyl-1-pentene.

Comparative Example RR

Reaction of equimolar mixture of EtMe₂ SiH/MeSiHCl₂ with 4-methyl-1-pentene.

In a 25 ml apparatus, there were combined 2.6 g (0.023 mol) of MeSiHCl₂, 2.0 g (0.023 mol) of EtMe₂ SiH, and 1.9 g (0.023 mol) of 4-methyl-1-pentene. A few droplets of Pt catalyst solution were added at 22° C. Gentle heating caused an exothermic reaction to 53° C. over 21 min., followed by heating at 50° C. for 130 min. VPC analysis of the complete reaction showed equivalent yields of MeSiCl₂ CH₂ CH₂ CH₂ CHMe₂ and EtMe₂ SiCH₂ CH₂ CH₂ CHMe₂. This example shows that while the promoting effect of EtMe₂ SiH is nearly equivalent to that of Et₃ SiH for the reaction of MeSiHCl₂ with 4-methyl-1-pentene, its competitive reactivity is significantly higher.

Comparative Example SS and Example 36

Reaction with Et₃ SiH with 3,3-dimethyl-1-butene promoted by Cl₃ SiH.

In a 50 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 8.4 g (0.01 mol) of 3,3-dimethyl-1-butene, and 0.01 ml Pt catalyst solution at 14° C. Heat was applied up to 86.5° C. over 113 min., when VPC analysis showed 38.4% conversion of reactants to Et₃ SiCH₂ CH₂ CMe₃. Reaction was cooled to 60° C. and 0.7 g (5 mol-%) of Cl₃ SiH added, causing a rapid exothermic reaction to 83° C. in 3 min., and complete conversion of reactants to Et₃ SiCH₂ CH₂ CMe₃. This example demonstrates both the low rate of the unpromoted reaction and the effectiveness of Cl₃ SiH as a promoter for the reaction between Et₃ SiH and 3,3-dimethyl-1-butene.

EXAMPLE 37

Reaction of equimolar mixture of Cl₃ SiH/Et₃ SiH with 3,3-dimethyl-1-butene.

In a 100 ml apparatus, there were combined 11.6 g (0.1 mol) of Et₃ SiH, 8.4 g (0.1 mol) of 3,3-dimethyl-1-butene, and 13.6 g (0.1 mol) of Cl₃ SiH. Pt Catalyst solution was added (0.05 ml) at 24° C., causing a rapid exothermic reaction to 57° C. in 4 min. Vacuum distillation yielded 1.82 g (8.3%) of Cl₃ SiCH₂ CH₂ CMe₃ and 11.95 g (59.8%) of Et₃ SiCH₂ CH₂ CMe₃. This example shows that Cl₃ SiH is an effective promoter at the equimolar level for the reaction between Et₃ SiH and 3,3-dimethyl-1-butene.

Comparative Example TT

Reaction of Et₃ SiH with allyl phenyl ether.

In a 50 ml apparatus, there were combined 10.1 g (0.075 mol) of allyl phenyl ether and 8.7 g (0.075 mol) of Et₃ SiH. Pt catalyst solution (0.02 ml) was added at 22° C., followed by heating up to 55° C. over 3 hrs. Vacuum stripping left 14.7 g (78.4%) of Et₃ SiCH₂ CH₂ CH₂ OC₆ H₅.

Example 38

Reaction of Et₃ SiH with allyl phenyl ether promoted by Cl₃ SiH.

The reaction of Comparative Example TT was repeated except that 1.4 g (0.01 mol) of Cl₃ SiH was also added. Gentle heating caused a violent exothermic reaction from 40° C. to 137° C. over 18 min. Vacuum stripping left 19.7 g (78.8%) of Et₃ SiCH₂ CH₂ CH₂ OC₆ H₅. This example shows that Cl₃ SiH is an effective promoter for the rate of the reaction between Et₃ SiH and allyl phenyl ether.

Comparative Example VV

Reaction of Et₃ SiH with methallyl phenyl ether.

In a 50 ml apparatus, there were combined 5.8 g (0.05 mol) of Et₃ SiH, 7.4 g (0.04 mol) of methallyl phenyl ether, and 0.02 ml of Pt catalyst solution at 21° C. Heat was applied to 86° C. over 115 min. VPC analysis showed only 21.9% conversion of reactants to Et₃ SiCH₂ CHMeCH₂ OC₆ H₅.

Example 39

Reaction of Et₃ SiH with methallyl phenyl ether promoted by Cl₃ SiH.

The reaction of Comparative Example VV was repeated except that 0.7 g (0.005 mol) of Cl₃ SiH was also added. There was a rapid exothermic reaction from 23° C. to 131° C. in 90 sec. VPC showed 88.4% conversion of reactants to Et₃ SiCH₂ CHMeCH₂ OC₆ H₅, demonstrating that Cl₃ SiH is a very effective promoter for the reaction of Et₃ SiH with methallyl phenyl ether. Note that the allyl and methallyl phenyl ethers are chemical models for allyl and methallyl polyalkylene oxide ethers which are articles of commerce.

Comparative Example WW

Reaction of Et₃ SiH with styrene.

In a 50 ml apparatus, there were combined 8.6 g (0.075 mol) of Et₃ SiH, 7.8 g (0.075 mol) of styrene, and 0.05 ml Pt catalyst solution at 20° C. There was a slow reaction to 29° C. over 33 min (heat rise due to magnetic stirrer), with VPC analysis showing 1.8% conversion of reactants to Et₃ SiCH₂ CH₂ C₆ H₅.

Example 40

Reaction of Et₃ SiH with styrene promoted by Cl₃ SiH.

The reaction of Comparative Example WW was repeated except that 1.0 g (0.0075 mol) of Cl₃ SiH was also added. There was an exothermic reaction to 39° C. over 38 min., with 24.1% conversion of reactants to Et₃ SiCHMeC₆ H₅ /Et₃ SiCH₂ CH₂ C₆ H₅ (0.59 molar ratio). This example shows that Cl₃ SiH is an effective promoter for the reaction between Et₃ SiH and styrene.

Comparative Example XX

Reaction of D₃ D' with vinyl acetate.

In a 100 ml apparatus, there were combined 30.5 g (0.1 mol) of 92% D₃ D' and 0.05 ml Pt catalyst solution. Heat was applied to 125° C. and addition of 8.6 g (0.1 mol) of vinyl acetate begun. Continued heating during addition caused an exothermic reaction to 195° C. over 220 min. Vacuum distillation yielded 11.42 g (31.0%) of D₃ D'CHMeOAc and 4.62 g (12.6%) of D₃ D'CH₂ CH₂ OAc.

EXAMPLE 41

Reaction of D₃ D' with vinyl acetate promoter by Cl₃ SiH.

The reaction of Comparative Example XX was repeated except that all reactants were combined at the start and 1.4 g (0.01 mol) of Cl₃ SiH was also added. Heat was applied to a maximum temp. of 147° C. over 360 min., followed by vacuum distillation, which yielded 5.46 g (14.8%) of D₃ D'CHMeOAc and 18.78 g (51.0%) of D₃ D'CH₂ CH₂ OAc. This example shows that Cl₃ SiH is an effective promoter for the reaction between D₃ D' and vinyl acetate, allowing reaction completion at significantly lower temp. with a much higher yield of the more stable and useful D₃ D'CH₂ CH₂ OAc isomer.

                                      TABLE XII                                    __________________________________________________________________________     PROMOTION USING OTHER OLEFINS                                                  Example                                                                               REACTANT A                                                                              OLEFIN     PROMOTER YIELD %                                                                              TIME                                 __________________________________________________________________________     Comp. OO                                                                              Et.sub.3 SiH                                                                            3-chloro-1-butene                                                                          --      7.6   70 min                               34     Et.sub.3 SiH                                                                            3-chloro-1-butene                                                                         18 mol % Cl.sub.3 SiH                                                                   73.6  52 min                               Comp. PP                                                                              Et.sub.3 SiH                                                                            4-methyl-1-pentene                                                                         --      11.0  7120                                                                              min                               35     Et.sub.3 SiH                                                                            4-methyl-1-pentene                                                                        10 mol % Cl.sub.3 SiH                                                                   29.7  8  min                               Comp. SS                                                                              Et.sub.3 SiH                                                                            3,3-dimethyl-1-butene                                                                      --      38.4  113                                                                               min                               36     Et.sub.3 SiH                                                                            3,3-dimethyl-1-butene                                                                     5 mol % Cl.sub.3 SiH                                                                    Comp.*                                                                               3  min                               37     Et.sub.3 SiH                                                                            3,3-dimethyl-1-butene                                                                     EqM. Cl.sub.3 SiH                                                                       59.8  4  min                               Comp. TT                                                                              Et.sub.3 SiH                                                                            allyl phenyl ether                                                                         --      78.4  >180                                                                              min                               38     Et.sub.3 SiH                                                                            allyl phenyl ether                                                                        13 mol % Cl.sub.3 SiH                                                                   78.8**                                                                               18 min                               Comp. VV                                                                              Et.sub.3 SiH                                                                            methallyl phenylether                                                                      --      21.9  115                                                                               min                               39     Et.sub.3 SiH                                                                            methallyl phenylether                                                                     10 mol % Cl.sub.3 SiH                                                                   88.4  11/2                                                                              min                               Comp. WW                                                                              Et.sub.3 SiH                                                                            Styrene     --      1.8   33 min                               40     Et.sub.3 SiH                                                                            Styrene    10 mol % Cl.sub.3 SiH                                                                   24.1  38 min                               Comp. XX                                                                              D.sub.3 D'                                                                              Vinyl acetate                                                                              --      12.6  220                                                                               min                               41     D.sub.3 D'                                                                              Vinyl acetate                                                                             10 mol % Cl.sub.3 SiH                                                                   51    360                                                                               min                               __________________________________________________________________________      *Run to Completion                                                       

This Table shows, except for the last 2 examples, the effect of Cl₃ SiH used as a promoter in a reaction between Et₃ SiH and various other olefins. In each case, this table shows clearly that small amounts (i.e., about 10 mol-%) of Cl₃ SiH significantly increases either rate or yield of these reactions. The last two examples show the same effect in a reaction between D₃ D' and vinyl acetate also promoted by Cl₃ SiH.

EXAMPLE 42

A 250 cc three-necked flask equipped with a 125 cc dropping addition funnel, magnetic stirrer, reflux condenser, thermometer, heating mantle, and nitrogen inlet was charged with 71.5 grams (0.638 moles) allyl acrylate, 0.150 grams phenothiazine inhibitor, 0.150 grams Diphenyl-p-phenylenediamine inhibitor and heated to 50° C. with stirring. When 50° C. was reached, 80 microliters of 10% chloroplatinic acid solution (20 ppm of platinum as based on total reaction charge) was injected into the flask followed by 100 microliters of triethylsilane promoter. A feed of trichlorosilane was introduced slowly to the olefin with continuous stirring over a period of two hours. An exotherm was apparent immediately at the start of the addition. An ice bath was necessary to maintain the reaction mixture between 50°-65° C. throughout the addition. A total of 78.5 grams (0.580 moles) of trichlorosilane was added. Following the complete addition, the reaction mixture was cooled to room temperature and samples for gas chromatographic analysis. Results indicated approximately 70% product of 3-acryloxypropyltrichlorosilane. The identification was verified later by gc/mass spec analysis. Recovery was 145 grams of reaction material.

This example shows the promotional effects of a second silane when the olefin is allyl acrylate. This reaction is important because the generated catalyst allows the reaction to occur at 50°-65° C., thus preventing the polymerization associated with usage of unstable acrylates at higher temperatures. While some product would form without promotion, it is uncertain when reaction initiation would occur. Thus the effective yield increase is great compared to the unpromoted reaction. 

I claim:
 1. In the process of preparing compounds containing silicon-carbon bonds by the hydrosilation reaction of a hydrosilyl reactant with an olefinic reactant in the presence of a soluble platinum catalyst, the improvement which comprises operating the process at a temperature below 150° C. and employing, as a reaction promoter, a hydrosilyl compound whereby said hydrosilyl reactant has a composition different from the composition of said promoter and whereby said promoter provides (i) a 20% increase in the amount of silicon-carbon compounds, or (ii) a 20% increase in reaction rate relative to an unpromoted reaction.
 2. The process according to claim 1 wherein said hydrosilyl reactant has the general formula R₃ SiH where each R is a monovalent hydrocarbon group, aliphatic having 1-10 carbon atoms or aromatic having 6-20 carbon atoms, free of terminal unsaturation, where said R group is unsubstituted or substituted with functional groups, with the proviso that when said hydrosilyl reactant is substituted to functional groups, said functional groups do not interfere in the promotion of the hydrosilation reaction.
 3. The process of claim 2 wherein R is selected from the group consisting of alkyl, aryl, alkoxy, acyloxy, and carbamoyloxy.
 4. The process according to claim 1 wherein said hydrosilyl reactant has the general formula R₃ SiH where R is halogen or siloxy.
 5. The process of claim 2 wherein the hydrosilyl reactant has a substituted functional group selected from the group consisting of halogen, cyano, carboalkoxy, ether, and thioether.
 6. The process of claim 2 wherein the hydrosilyl reactant has at least two R groups to form a heterocyclic ring including the silicon.
 7. The process of claim 6 wherein the hydrosilyl reactant is ##STR8## where n=3-6.
 8. The process according to claim 1 wherein the hydrosilyl promoter has the general formula R₃ SiH where each R represents a monovalent hydrocarbon group, aliphatic having 1-10 carbon atoms or aromatic having 6-20 carbon atoms free of terminal unsaturation, where said R group is unsubstituted or substituted with functional groups, with the proviso that when said hydrosilyl promoter is substituted to form functional groups, said functional groups do not interfere in the promotion of the hydrosilation reaction.
 9. The process of claim 8 wherein R is selected from the group consisting of alkyl, aryl, alkoxy, acyloxy and carbamoyloxy.
 10. The process according to claim 1 wherein the hydrosilyl promoter has the general formula R₃ SiH where R represents halogen or siloxy.
 11. The process of claim 8 wherein the hydrosilyl promoter has a substituted functional group selected from the group consisting of halogen, cyano, carboalkoxy, ether and thioether.
 12. The process according to claim 1 wherein said promoter is selected from the group consisting of Cl₃ SiH, MeSiHCl₂, Me₂ SiHCl, Et₃ SiH, F₃ SiH and Br₃ SiH.
 13. The process according to claim 1 where the promoter is Cl₃ SiH and the hydrosilyl reactant is (CH₃ CH₂)₃ SiH.
 14. The process according to claim 1 where the promoter is (CH₃ CH₂)₃ SiH and the hydrosilyl reactant is Cl₃ SiH.
 15. The process according to claim 1 where the promoter is (CH₃ CH₂)₃ SiH and the hydrosilyl reactant is (CH₃ O)₃ SiH.
 16. The process according to claim 1 wherein the olefinic reactant has the general formula CH₂ ═C<.
 17. The process of claim 16 wherein the olefin is selected from the group consisting of allyl and methallyl compounds, vinyl compounds, terminal alkenes, including halides, ethers, esters and nitriles, with the proviso that when the olefinic reactant is substituted to functional groups, said functional groups do not interfere with the hydrosilation reaction.
 18. The process according to claim 16 wherein the olefinic reactant is an allyl or methallyl polyalkylene oxide ether.
 19. The process according to claim 16 wherein the olefinic reactant is allyl acrylate.
 20. The process according to claim 1 wherein said reaction is run at sub-ambient temperatures.
 21. The process of claim 1 wherein said soluble platinum compound is chosen from the group consisting of solutions of H₂ PtCl₆, in hydrated or unhydrated form, solutions of PtCl₄ or PtCl₂ and solutions of ethylene bis (platinum chloride).
 22. The process of claim 1 wherein said reaction promoter is used at 0.0001-2.0 molar amounts relative to the hydrosilyl reactant, and said reactant containing carbon-carbon olefinic unsaturation is used at 0.1-2.0 molar amounts relative to the silicon-bonded hydrogen reactant. 